CN103718109A

CN103718109A - Photosensitive resin composition, material for forming relief pattern, photosensitive film, polyimide film, cured relief pattern and method for producing same, and semiconductor device

Info

Publication number: CN103718109A
Application number: CN201280037948.3A
Authority: CN
Inventors: 和田健二; 荒山恭平; 雨宫拓马
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2011-07-29
Filing date: 2012-07-12
Publication date: 2014-04-09
Anticipated expiration: 2032-07-12
Also published as: WO2013018524A1; JP2013050696A; JP5887172B2; CN103718109B; KR101780663B1; KR20140047105A

Abstract

Provided are: a photosensitive resin composition which has lithographic performance including excellent resolution and excellent sensitivity and enables the formation of a cured relief pattern that has low stress and therefore can prevent the warpage of a wafer in so-called low-temperature curing; a material for forming a relief pattern, a photosensitive film, a polyimide film, a cured relief pattern and a method for producing the cured relief pattern, each of which utilizes the photosensitive resin composition; and a semiconductor device involving the cured relief pattern. A photosensitive resin composition comprising (a) a resin having a repeating unit represented by general formula (1) and (b) a compound capable of generating an acid upon the irradiation with an active ray or a radioactive ray. In general formula (1), R1's independently represent a tetravalent organic group, wherein the multiple R1's may be the same as or different from each other; R2's independently represent a bivalent organic group, wherein the multiple R2's may be the same as or different from each other, and wherein at least one of the multiple R2's is a bivalent organic group having an alicyclic group; and R3's independently represent a hydrogen atom or an organic group, wherein at least one of multiple -CO2R3 groups is a group capable of being decomposed by the action of an acid to produce an alkali-soluble group.

Description

Photosensitive polymer combination, relief pattern form material, photosensitive film, polyimide film, sclerosis relief pattern, its manufacture method and semiconductor device

Technical field

The present invention relates to the interlayer dielectric that a kind of surface protection film as semiconductor device, interlayer dielectric, display element use and the eurymeric high-fire resistance photosensitive polymer combination using used the manufacture method of the stable on heating sclerosis relief pattern of having of this eurymeric high-fire resistance photosensitive polymer combination (relief pattern) and the semiconductor device that contains relief pattern.

Background technology

For surface protection film, the interlayer dielectric of semiconductor device, use the minus polyimide resin have excellent thermotolerance and electrical specification, mechanical property etc. concurrently always.This minus polyimide resin normally provides with the form of photosensitive polyimide precursor composition at present; there is following characteristics: can be coated with by enforcement, utilize the patterning, organic solvent of active ray (active ray) to develop, the hot-imide processing under high temperature etc.; and on semiconductor device, easily form surface protection film, interlayer dielectric etc.; compare with existing non-photosensitive polyimide precursor composition, can shorten significantly step.

Yet photosensitive minus polyimide precursor composition must be used a large amount of organic solvent such as METHYLPYRROLIDONE as developer solution in its development step, due to the aggravation of environmental problem in recent years etc., and seek de-organic solvent countermeasure.Corresponding to this, various and photoresist (photoresist) the thermotolerance photoresist material that similarly utility alkali aqueous solution is developed has been proposed recently.

Wherein, following methods receives publicity in recent years, and the method is used using the composition of the photolytic activity composition mixing gained such as the polyamic acid of alkaline aqueous solution solubility (polyimide precursor) or hydroxypolyamide (polybenzoxazoles) precursor and photonasty diazonium naphtoquinone compounds as positive type photosensitive organic compound.

The developing machine of this normal Photosensitive resin is built in utilizing following situation: the photonasty diazonium naphtoquinone compounds of unexposed portion is insoluble to alkaline aqueous solution, with respect to this, this photonasty diazonium naphtoquinone compounds generation chemical change by exposing, becomes indeno carboxylic acid (indene carboxylic acid) compound and becomes and dissolve in alkaline aqueous solution.Utilize between this exposure portion and unexposed portion poor to the dissolution velocity of developer solution, can carry out the only formation of the relief pattern of unexposed portion (for example, with reference to patent documentation 1).

On the other hand, as the technology that photonasty and the insoluble function of unexposed portion are separated, in the field of the photic resist of semiconductor, widely apply the photosensitive composite of chemical amplification type, the photosensitive composite of this chemical amplification type produces the acid of catalytic amount by exposing, then pass through heating process, the chemical reaction of utilization using the acid being produced by exposure as catalyzer, changes the insoluble base of the alkali in composition into alkali soluble base.In this technical field, also disclosed the photosensitive composite (for example, with reference to patent documentation 2) of chemical amplification type.With regard to the viewpoint of high resolving power (resolution), high sensitivity (sensitivity) etc., disclose the photosensitive polymer combination (for example, with reference to patent documentation 3, patent documentation 4) that has the chemical amplification type that contains the polyimide precursor of protecting through the specific protecting group of sour decomposability especially.

On the other hand, be accompanied by recent years the development of semiconductor technology, require the formation of finer pattern and reduce the dura mater temperature (solidification temperature) after pattern forms.

Yet known, when having reduced the situation of solidification temperature, acid imide cyclisation is difficult for carrying out.About this problem, such as having reported by adding sulfonic acid, sulfonate compound etc., improve (patent documentation 5).Yet known, also exist the film strength of gained or chemical-resistant not enough, or undermine the situation of the formation ability of fine image.

In addition, be accompanied by heavy caliber, the lamination of silicon wafer in recent years, be formed with the also apparition of problem of the warpage (below also referred to as " chip warpage ") of the silicon wafer of polyimide film.It is generally acknowledged, this warpage is due to the residual stress being produced by the coefficient of thermal expansion differences because of polyimide and silicon wafer, thus tight demand compared with existing polyimide the polyimide (for example, with reference to non-patent literature 1) for low heat expansion, low stress (low stress) property.By polyimide main chain being set as to straight line and upright and outspoken structure, can realize low heat expansion (with reference to non-patent literature 2), but this kind of structure has following problem: the i radiolucency of its precursor, solvent solubility, alkali dissolubility are low, cannot give sufficient micro-shadow (lithography) performance etc.For example, in patent documentation 6, disclose and have a kind of polyphenyl oxazole (Polybenzoxazole that contains, PBO) positive light sensitivity composition of precursor, it contains acidic compound and PBO precursor by radioactive ray (radioactive ray) irradiation, and the residual stress by the formed polybenzoxazoles film of above-mentioned PBO precursor is below 25MPa, but this positive light sensitivity composition exists variety of issue at micro-shadow aspect of performances such as sensitivity, profiles (profile).

Prior art document

Patent documentation

Patent documentation 1: the clear 56-27140 communique of Japanese Patent Laid-Open

Patent documentation 2: Japanese Patent Laid-Open 2002-526793 communique

Patent documentation 3: Japanese Patent Laid-Open 2009-244479 communique

Patent documentation 4: Japanese Patent Laid-Open 2009-192760 communique

Patent documentation 5: Japanese Patent Laid-Open 2006-010781 communique

Patent documentation 6: Japanese Patent Laid-Open 2001-214055 communique

Non-patent literature

Non-patent literature 1: light polymers science and technology periodical (J.Photopolym.Sci.Technol.) VOL.15; No.2; 167-172 page (2002)

Non-patent literature 2: up-to-date polyimide～basis and application～(Japanese polyimide research association compile)

Summary of the invention

The problem that invention will solve

The object of the present invention is to provide a kind of photosensitive polymer combination, use relief pattern formation material, photosensitive film, polyimide film, sclerosis relief pattern, its manufacture method of this photosensitive polymer combination and the semiconductor device that contains this sclerosis relief pattern, above-mentioned photosensitive polymer combination has micro-shadow performance of resolution and sensitivity excellence, under sclerosis under the low temperature (being preferably below 250 ℃) below 300 ℃, so-called low-temperature setting, stress is low, can form thus the sclerosis relief pattern that prevents chip warpage.

The technological means of dealing with problems

The present invention is following formation, has solved thus above-mentioned problem of the present invention.

[1] photosensitive polymer combination, it contains:

(a) have the represented repetitive of following general formula (1) resin and

(b) the acidic compound by the irradiation of active ray or radioactive ray,

[changing 1]

In above-mentioned general formula (1),

R ¹represent quadrivalent organic radical; A plurality of R ¹can be mutually the same also can be different;

R ²represent divalent organic base; A plurality of R ²can be mutually the same also can be different;

Wherein, a plurality of R ²in at least one is the divalent organic base that contains alicyclic group;

R ³independently represent respectively hydrogen atom or organic group;

Wherein, a plurality of-CO ₂r ³in there is to decompose the base that produces alkali-soluble base for effect by sour at least one.

[2] photosensitive polymer combination as described in [1], wherein the above-mentioned resin (a) with the represented repetitive of general formula (1) is for having the resin of the represented repetitive of the represented repetitive of following general formula (2) and following general formula (3)

[changing 2]

In above-mentioned general formula (2),

R ¹' with above-mentioned general formula (1) in R ¹for identical meanings;

R ³' with above-mentioned general formula (1) in R ³for identical meanings;

Wherein, a plurality of-CO ₂r ³' in there is to decompose the base that produces alkali-soluble base for effect by sour at least one;

R ⁴for containing the divalent organic base of alicyclic group;

In above-mentioned general formula (3),

R ¹" with the R in above-mentioned general formula (1) ¹for identical meanings;

R ³" with the R in above-mentioned general formula (1) ³for identical meanings;

Wherein, a plurality of-CO ₂r ³" in there is to decompose the base that produces alkali-soluble base for effect by sour at least one;

R ⁵for with R ⁴different divalent organic bases.

[3] photosensitive polymer combination as described in [2], the wherein R in above-mentioned general formula (3) ⁵for containing the bivalent radical of aromatic series base.

[4] photosensitive polymer combination as described in [3], the wherein R in above-mentioned general formula (3) ⁵for any represented bivalent radical of following formula,

[changing 3]

In above-mentioned formula, the hydrogen atom of each aromatic rings can be respectively independently at least one atom or the base in selecting the cohort that free fluorine atom, chlorine atom, bromine atoms, methyl, methoxyl, cyano group, phenyl and trifluoromethyl form replace.

[5] photosensitive polymer combination as described in any one in [1] to [4], wherein in above-mentioned general formula (1)-CO ₂r ³, in above-mentioned general formula (2)-CO ₂r ³' or above-mentioned general formula (3) in-CO ₂r ³" heat decomposition temperature be 100 ℃～220 ℃.

[6] photosensitive polymer combination as described in any one in [1] to [5], wherein in above-mentioned general formula (1)-CO ₂r ³, in above-mentioned general formula (2)-CO ₂r ³' or above-mentioned general formula (3) in-CO ₂r ³" the sour effect passed through occur to decompose and produce hydrogen atom that the base of alkali-soluble base is carboxyl through the ester group of the represented base replacement of following general formula (III),

[changing 4]

In above-mentioned general formula,

Ra represents hydrogen atom, alkyl, naphthenic base, aryl or aralkyl;

Rb represents singly-bound or bivalence linking base;

Q represents alkyl, can contain heteroatomic alicyclic group, maybe can contain heteroatomic fragrant cyclic group;

Ra, Rb and Q at least two also bonds and form ring mutually.

[7] photosensitive polymer combination as described in [6], wherein the Ra in above-mentioned general formula (III) is following general formula (IV) or the represented base of general formula (V),

[changing 5]

In above-mentioned general formula,

Rc, Rd, Re, Rf and Rg be independent alkyl, naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkoxy carbonyl, aryloxycarbonyl, cyano group or the halogen atom of representing respectively, Rc and Rd be bond and form ring mutually also, Re, Rf and Rg at least two also bonds and form ring mutually.

[8] photosensitive polymer combination as described in [7], wherein at least one of the Rc in above-mentioned general formula (IV) and Rd is naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkoxy carbonyl, aryloxycarbonyl, cyano group or halogen atom.

[9] photosensitive polymer combination as described in [8], wherein at least one of the Rc in above-mentioned general formula (IV) and Rd is aryl.

[10] photosensitive polymer combination as described in [6], wherein at least one of Ra, the Rb in above-mentioned general formula (III) and Q is electrophilic base or the base that contains electrophilic base.

[11] photosensitive polymer combination as described in [1], the wherein R in above-mentioned general formula (1) ¹for the fatty group that contains monocyclic or condensation polycyclic formula or the tetravalence concatenating group of aromatic series base.

[12] photosensitive polymer combination as described in [1] or [11], the wherein R in above-mentioned general formula (1) ²for the bivalent radical that contains alicyclic group, the bivalent radical that contains aromatic series base or the bivalent radical that contains silicon atom.

[13] photosensitive polymer combination as described in any one in [1] to [12], wherein the quality mean molecular weight of above-mentioned resin (a) is below 200,000.

[14] photosensitive polymer combination as described in any one in [1] to [13], it also contains (c) alkali compounds.

[15] photosensitive polymer combination as described in any one in [1] to [14], wherein above-claimed cpd (b) is oxime compound.

[16] photosensitive polymer combination as described in any one in [1] to [15], it also contains (f) and connects airtight promoter.

[17] photosensitive polymer combination as described in any one in [1] to [16], it develops and uses for eurymeric.

[18] pattern forming material, it is the photosensitive polymer combination as described in any one in [1] to [16].

[19] photosensitive film, it is to form by the photosensitive polymer combination as described in any one in [1] to [16].

[20] polyimide film, it is that the photosensitive polymer combination as described in any one in [1] to [16] is carried out heat treated and obtained.

[21] the harden manufacture method of relief pattern, it comprises the following steps:

(A) on substrate, form the step of the photosensitive film as described in [19];

(B) step of utilizing active ray or radioactive ray to expose to this photosensitive film;

(C) step that the mode of in order to use alkaline developer, this photosensitive film being removed through the part of exposure is developed; And

(D) relief pattern of gained is carried out to the step of heat treated.

[22] a sclerosis relief pattern, it is to obtain by the manufacture method as described in [21].

[23] semiconductor device, it possesses the sclerosis relief pattern as described in [22].

[24] resin, it has the represented repetitive of following general formula (1),

[changing 6]

In above-mentioned general formula (1),

R ³independently represent respectively hydrogen atom or organic group;

The effect of invention

Photosensitive polymer combination of the present invention has micro-shadow performance of resolution and sensitivity excellence, and under so-called low-temperature setting, stress is low, can form thus the sclerosis relief pattern that prevents chip warpage.

According to the present invention, the semiconductor device that can provide a kind of relief pattern to form material, photosensitive film, polyimide film, sclerosis relief pattern, its manufacture method and contain this sclerosis relief pattern, above-mentioned relief pattern forms micro-shadow performance that material has resolution and sensitivity excellence, low stress excellent under so-called low-temperature setting, can form the sclerosis relief pattern that prevents chip warpage.

Embodiment

In the statement of base in this manual (atomic group), do not record the statement be substituted and be unsubstituted and not only refer to not there is substituent base, and also comprise and there is substituent base.For example so-called " alkyl ", not only refers to and does not have substituent alkyl in (alkyl being unsubstituted), also comprises and has substituent alkyl in (alkyl being substituted).

In this instructions so-called " active ray " or " radioactive ray ", for example refer to the bright-line spectrum of mercury vapor lamp, the far ultraviolet of excimer laser representative, Extreme Ultraviolet (Extreme Ultraviolet, EUV light), X ray, electron beam (Electron Beam, EB) etc.In addition, so-called light in the present invention, refers to active ray or radioactive ray.

In addition, in this instructions, what is called " exposure " as long as no special instructions, not only refer to the exposure that far ultraviolet, extreme ultraviolet line, X ray, EUV light of utilizing mercury vapor lamp, excimer laser representative etc. carry out, utilize the drawing of the particle beams such as electron beam, ion beam to be also included within exposure.

Photosensitive polymer combination of the present invention contains: (a) have the represented repetitive of following general formula (1) resin and

(b) the acidic compound by the irradiation of active ray or radioactive ray.

[changing 7]

In above-mentioned general formula (1),

R ¹represent quadrivalent organic radical.A plurality of R ¹can be mutually the same also can be different.

R ²represent divalent organic base.A plurality of R ²can be mutually the same also can be different.

Wherein, a plurality of R ²in at least one is the divalent organic base that contains alicyclic group.

R ³independently represent respectively hydrogen atom or organic group.

The photosensitive polymer combination of the present invention that contains the resin (a) with the represented repetitive of above-mentioned general formula (1) has micro-shadow performance of resolution and sensitivity excellence, under so-called low-temperature setting, stress is low, can form thus the sclerosis relief pattern that prevents chip warpage, though its reason is uncertain, is generally presumed as follows.

The represented repetitive of above-mentioned general formula (1) can form rectilinearity and upright and outspoken polyimide by thermmohardening, and then, by being present in a plurality of R in resin (a) ²in at least one is set as the divalent organic base that contains alicyclic group, can improve rectilinearity and outspoken nature.General supposition, can reduce thermal expansivity thus especially, can realize low stress, thereby can prevent chip warpage.

And then infer, be present in a plurality of R in resin (a) ²in at least one is the divalent organic base that contains alicyclic group, thus in the situation that do not undermine the transmitance of the i ray etc. in when exposure, realize micro-shadow performance of resolution and sensitivity excellence.

(a) there is the resin of the repetitive of general formula (1)

The resin (a) with the represented repetitive of above-mentioned general formula (1) is the resin of the effect by sour to the solubleness increase of alkaline developer.It is insoluble or slightly solubility that the resin with the repetitive of general formula (1) is preferably in alkaline developer.

The represented repetitive of general formula (1) comprises sour composition and two amine components, and above-mentioned sour composition is to derive from R ¹for core has hydrogen atom at least one in compound, its carboxylic acid anhydrides or above-mentioned 4 carboxyls of 4 carboxyls base through departing from by sour effect, replace the compound forming, above-mentioned two amine components are to derive from R ²for core has 2 amino compounds.In other words, the represented repetitive of general formula (1) comprise sour composition as the part-structure that comprises these 2 carbonyls of 2 carbonyls clamping in above-mentioned general formula (1), with as in above-mentioned general formula (1)-NH-R ²two amine components of the part-structure that-NH-is represented.

Quadrivalent organic radical R ¹being preferably carbon number is 4～30, more preferably contains the fatty group of monocyclic or condensation polycyclic formula or the tetravalence concatenating group of aromatic series base.Be present in a plurality of R in resin (a) ¹can be mutually the same also can be different.

Quadrivalent organic radical R ¹in the aromatic series base of monocyclic can enumerate phenyl ring base, pyridine cyclic group etc.

Quadrivalent organic radical R ¹in the aromatic series base of condensation polycyclic formula can enumerate naphthalene nucleus Ji, perylene cyclic group etc.

Quadrivalent organic radical R ¹in the fatty group of monocyclic can enumerate cyclo-butane cyclic group, cyclopentane cyclic group, cyclohexane cyclic group etc.

Quadrivalent organic radical R ¹in the fatty group of condensation polycyclic formula can enumerate dicyclo [2.2.1] heptane cyclic group, dicyclo [2.2.2] octane cyclic group, dicyclo [2.2.2] pungent-7-alkene cyclic group etc.

About quadrivalent organic radical R ¹the fatty group that contains monocyclic or condensation polycyclic formula or the tetravalence concatenating group of the aromatic series base fatty group or the basic body of aromatic series that also can be above-mentioned monocyclic or condensation polycyclic formula, also can the fatty group of a plurality of monocyclics or condensation polycyclic formula or aromatic series base be linked via singly-bound or bivalence linking base, form as R ¹tetravalence concatenating group.

Above-mentioned bivalence linking base can be enumerated: alkylidene (being preferably carbon number and being 1～6 alkylidene, such as methylene, ethylidene, propylidene etc.), oxygen atom, sulphur atom, divalence sulfuryl, ester bond, ketone group, amide group etc.

With R ¹the concrete example for core with the sour composition of at least 4 bases that derive from carboxyl can be enumerated: derive from pyromellitic dianhydride, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid acid anhydride, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic anhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic anhydride, 4,4 '-(hexafluoroisopropyli,ene) diphthalic anhydrides, 1,2,5,6-naphthalene tetracarboxylic acid acid anhydride, 2,3,6,7-naphthalene tetracarboxylic acid acid anhydride, 2,3,5,6-pyridine tetracarboxylic anhydride, 3,4,9,10-perylene tetracarboxylic acid acid anhydride, (trifluoromethyl) pyromellitic dianhydride, two (trifluoromethyl) pyromellitic dianhydride, two (seven fluoropropyls) pyromellitic dianhydride, pentafluoroethyl group pyromellitic dianhydride, two [3,5-bis-(trifluoromethyl) phenoxy group] pyromellitic dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, 2,3 ', 3,4 '-tetracarboxylic diphenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl methane dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl sulfone dianhydride, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2,2-, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2,2-, 5,5 '-bis-(trifluoromethyl)-3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydride, 2,2 ', 5,5 '-tetra-(trifluoromethyl)-3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydride, 5,5 '-bis-(trifluoromethyl)-3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, 5,5 '-bis-(trifluoromethyl)-3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, two [(trifluoromethyl) di carboxyl phenyloxy] benzene dianhydride, two (di carboxyl phenyloxies) two (trifluoromethyl) benzene dianhydride, two (di carboxyl phenyloxies) four (trifluoromethyl) benzene dianhydride, two [4-(3,4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2,2-, two (4-(3, the 4-di carboxyl phenyloxy) phenyl) hexafluoropropane dianhydrides of 2,2-, the composition of 5,5 '-aromatic tetracarboxylic acid's acid anhydrides such as [TOPOT 2,2′ p phenylenebis (oxygen base carbonyl)] diphthalic anhydrides, or derive from cyclo-butane tetracarboxylic anhydride, cyclopentane tetracarboxylic anhydride, cyclohexane tetracarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid, dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid, dicyclo [2.2.2] octane-2,3,5,6-tetrabasic carboxylic acid, or dicyclo [2.2.2] pungent-7-alkene-2,3,5,6-tetrabasic carboxylic acid, dicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, (1S, 2S, 4R, 5R)-cyclohexane tetracarboxylic dianhydride, the one-tenth of (1R, 2S, 4S, 5R)-aliphatics tetracarboxylic anhydrides such as cyclohexane tetracarboxylic dianhydride grades.

Be preferably the composition that derives from pyromellitic dianhydride, derive from 3, 3 ', 4, the composition of 4 '-biphenyltetracarboxyacid acid acid anhydride, derive from 2, 3, 3 ', the composition of 4 '-biphenyltetracarboxyacid acid acid anhydride, derive from 2, 2 ', 3, the composition of 3 '-biphenyltetracarboxyacid acid acid anhydride, derive from 3, 3 ', 4, the composition of 4 '-benzophenone tetracarboxylic anhydride, derive from 4, the composition of 4 '-(hexafluoroisopropyli,ene) diphthalic anhydrides, derive from 3, 3 ', 4, the composition of 4 '-tetracarboxylic diphenyl ether dianhydride, derive from 1, 2, 5, the composition of 6-naphthalene tetracarboxylic acid acid anhydride, derive from 5, the composition of 5 '-[TOPOT 2,2′ p phenylenebis (oxygen base carbonyl)] diphthalic anhydrides, derive from the composition of cyclo-butane tetracarboxylic anhydride, derive from the composition of cyclopentane tetracarboxylic anhydride, derive from dicyclo [2.2.2] octane-2, 3, 5, 6-tetracarboxylic dianhydride's composition, derive from (1S, 2S, 4R, 5R)-cyclohexane tetracarboxylic dianhydride's composition, derive from (1R, 2S, 4S, 5R)-cyclohexane tetracarboxylic dianhydride's composition,

More preferably derive from the composition of pyromellitic dianhydride, derive from 3, 3 ', 4, the composition of 4 '-biphenyltetracarboxyacid acid acid anhydride, derive from 4, the composition of 4 '-(hexafluoroisopropyli,ene) diphthalic anhydrides, derive from the composition of cyclo-butane tetracarboxylic anhydride, derive from 3, 3 ', 4, the composition of 4 '-tetracarboxylic diphenyl ether dianhydride, derive from the composition of cyclopentane tetracarboxylic anhydride, derive from 5, the composition of 5 '-[TOPOT 2,2′ p phenylenebis (oxygen base carbonyl)] diphthalic anhydrides, derive from (1S, 2S, 4R, 5R)-cyclohexane tetracarboxylic dianhydride's composition, derive from (1R, 2S, 4S, 5R)-cyclohexane tetracarboxylic dianhydride's composition.By using these compositions, can realize good solvent solubility, alkali dissolution velocity, the transparency, stress characteristics.

All repetitives with respect to forming resin (a), derive from R ¹the content of the sour composition of compound etc. that has 4 carboxyls for core in resin (a) is preferably 20mol%～70mol%, more preferably 30mol%～60mol%.

Divalent organic base R ²bivalent radical that can enumerate the bivalent radical that contains alicyclic group, the bivalent radical that contains aromatic series base, contains silicon atom etc.Be present in a plurality of R in resin (a) ²can be mutually the same also can be different.

Below, sometimes also by R ²for contain alicyclic group bivalent radical time with R ²for two amine components of core are called alicyclic diamine composition, sometimes also by R ²for contain aromatic series base bivalent radical time with R ²for two amine components of core are called aromatic diamine composition, sometimes also by R ²for contain silicon atom bivalent radical time with R ²for two amine components of core are called silicon two amine components.

Be present in the R in a plurality of two amine components in resin (a) ²in at least one is the bivalent radical that contains alicyclic group.By resin (a), contain two amine components with alicyclic group, can realize good solvent solubility, alkali dissolution velocity, the transparency, sensitivity.

R ²it is 3～20 divalence alicyclic group that the alicyclic group that can contain is preferably carbon number, can enumerate: the cycloalkylidene of the monocycles such as cyclopentylene, cyclohexylidene, the cycloalkylidene of many rings such as sub-dicyclo [2.2.1] heptyl, sub-norborny, sub-Fourth Ring decyl, sub-Fourth Ring dodecyl, sub-adamantyl etc.

About R ²the bivalent radical that contains alicyclic group also can be above-mentioned alicyclic group itself, also can utilize alkylidene (being preferably carbon number and being 1～6 alkylidene, such as methylene, ethylidene, propylidene etc.) that a plurality of alicyclic groups are linked, form as R ²the bivalent radical that contains alicyclic group, also can utilize alkylidene that the amino in two amine components and alicyclic group are linked.

Above-mentioned alicyclic group, the alkylidene that can form the bivalent radical that contains alicyclic group also can have substituting group, and this kind of substituting group can be enumerated alkyl (be preferably carbon number be 1～4 alkyl), halogen atom etc.

Particularly preferred with R ²for two amine components with alicyclic group structure of core can be enumerated: 5-amino-1, 3, 3-trimethyl-cyclohexane methyl amine composition, cis-1, 4-cyclohexane diamine composition, anti-form-1, 4-cyclohexane diamine composition, 1, 4-cyclohexane diamine composition (cis, trans potpourri), 4, 4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine) composition and 3, 3 '-dimethyl substituent, two (amino methyl) dicyclo [2.2.1] heptane composition, 1, 3-diamido diamantane composition, 3, 3 '-diaminostilbene, 1 '-Lian diamantane composition, 4, two (cyclo-hexylamine) compositions of 4 '-hexafluoroisopropyli,ene, wherein with regard to the viewpoint of reduction stress, be preferably 3, 3 '-diaminostilbene, 1 '-Lian diamantane composition, anti-form-1, 4-cyclohexane diamine composition.

With respect to all repetitives that form resin (a), with R ²for having the content of 2 amino alicyclic diamine compositions in resin (a), core is preferably 20mol%～70mol%, more preferably 30mol%～60mol%.

About R ²the bivalent radical that contains aromatic series base in aromatic series base to be preferably carbon number be 5～16 aromatic series base, can enumerate phenylene, naphthylene etc.In addition, above-mentioned aromatic series base also can contain the heteroatomss such as nitrogen-atoms, oxygen atom, such as enumerating divalence benzoxazolyl etc.

About R ²the bivalent radical that contains aromatic series base also can be the basic body of above-mentioned aromatic series, also can a plurality of aromatic series bases be linked via singly-bound or bivalence linking base, form as R ²the bivalent radical that contains aromatic series base, also can the amino in two amine components and aromatic series base be linked via bivalence linking base.

Above-mentioned aromatic series base, the alkylidene that can form the bivalent radical that contains aromatic series base also can have substituting group, and this kind of substituting group can be enumerated: aryl such as alkoxy, cyano group, phenyl such as alkyl (be preferably carbon number be 1～4 alkyl), halogen atom, methoxyl etc.

About with R ²for the concrete example of the aromatic diamine composition of core, for example, can enumerate: m-phenylene diamine composition, p-phenylenediamine (PPD) composition, 2,4-toluene diamine composition, 3,3 '-diamino-diphenyl ether composition, 3,4 '-diamino-diphenyl ether composition, 4,4 '-diamino-diphenyl ether composition, 3,3 '-diamino diphenyl sulfone composition, 4,4 '-diamino diphenyl sulfone composition, 3,4 '-diamino diphenyl sulfone composition, 3,3 '-diaminodiphenyl-methane composition, 4,4 '-diaminodiphenyl-methane composition, 3,4 '-diaminodiphenyl-methane composition, 4,4 '-diamino-diphenyl thioether composition, 3,3 '-diamino-diphenyl ketone composition, 4,4 '-diamino-diphenyl ketone composition, 3,4 '-diamino-diphenyl ketone composition, 2,2 '-bis-(4-aminophenyl) propane composition, 2,2 '-bis-(4-aminophenyl) HFC-236fa composition, two (3-amino-benzene oxygen) the benzene compositions of 1,3-, two (4-amino-benzene oxygen) the benzene compositions of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene composition, 4-methyl-2, two (4-the aminophenyl)-1-amylene compositions of 4-, 4-methyl-2, two (4-the aminophenyl)-2-amylene compositions of 4-, Isosorbide-5-Nitrae-bis-(α, alpha-alpha-dimethyl-4-aminobenzyl) benzene composition, imino group-di P phenylene diamine composition, 1,5-diaminonaphthalene composition, 2,6-diaminonaphthalene composition, 4-methyl-2, two (4-aminophenyl) the pentane compositions of 4-, 5 (or 6)-amino-1-(4-aminophenyl)-1,3,3-trimethyl indenes alkane composition, two (p-aminophenyl) phosphine oxide composition, 4,4 '-chrysoidine composition, 4,4 '-diamino-diphenyl urea composition, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl composition, two [4-(4-amino-benzene oxygen) phenyl] the propane compositions of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] the HFC-236fa compositions of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] the benzophenone compositions of 2,2-, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfone composition, 4,4 '-bis-[4-(α, alpha-alpha-dimethyl-4-aminobenzyl) phenoxy group] benzophenone composition, 4,4 '-bis-[4-(α, alpha-alpha-dimethyl-4-aminobenzyl) phenoxy group] diphenyl sulfone composition, 4,4 '-benzidine composition, 4,4 '-diaminobenzophenone composition, phenylindan alkane two amine components, 3,3 '-dimethoxy-4 ', 4 '-benzidine composition, 3,3 '-dimethyl-4,4 '-benzidine composition, 2,2 '-dimethyl 4,4 '-benzidine composition, 2,2 '-bis-(trifluoromethyl) biphenylamine composition, ortho-aminotoluene sulfone composition, two (4-amino-benzene oxygen phenyl) the propane compositions of 2,2-, two (4-amino-benzene oxygen phenyl) sulfone composition, two (4-amino-benzene oxygen phenyl) thioether composition, Isosorbide-5-Nitrae-(4-amino-benzene oxygen phenyl) benzene composition, 1,3-(4-amino-benzene oxygen phenyl) benzene composition, two (4-aminophenyl) the fluorenes compositions of 9,9-, 4,4 '-bis--(3-amino-benzene oxygen) diphenyl sulfone compositions, 4,4 '-diaminobenzene formailide composition, the amino phenyl ester composition of 4 '-aminophenyl benzoic acid-4-, two (4-aminophenyl) the ester compositions of terephthalic acid (TPA), 2-(4-aminophenyl) benzoxazoles-5-base amine, 4,4 " diamido-para-terpheny becomes to grade, and the hydrogen atom of the aromatic proton of these aromatic diamines is through selecting free chlorine atom, fluorine atom, bromine atoms, methyl, methoxyl, cyano group, at least one base in the cohort that phenyl forms or atom replace the structure forming.

Particularly preferred aromatic diamine composition can be enumerated: p-phenylenediamine (PPD) composition, 4,4 '-diamino-diphenyl ether composition, 3,3 '-diamino diphenyl sulfone composition, 4,4 '-diamino diphenyl sulfone composition, 2,2 '-bis-(4-aminophenyl) HFC-236fa composition, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene composition, imino group-di P phenylene diamine composition, 4,4 '-benzidine composition, 4,4 '-diaminobenzophenone composition, 3,3 '-dimethoxy-4 ', 4 '-benzidine composition, 3,3 '-dimethyl-4,4 '-benzidine composition, 2,2 '-dimethyl 4,4 '-benzidine composition, 2,2 '-bis-(trifluoromethyl) biphenylamine composition, ortho-aminotoluene sulfone composition, two (4-amino-benzene oxygen phenyl) the propane compositions of 2,2-, two (4-aminophenyl) the fluorenes compositions of 9,9-, 4,4 '-bis--(3-amino-benzene oxygen) diphenyl sulfone compositions, 4,4 '-diaminobenzene formailide composition, the amino phenyl ester composition of 4 '-aminophenyl benzoic acid-4-, two (4-aminophenyl) esters of terephthalic acid (TPA), 2-(4-aminophenyl) benzoxazoles-5-base amine component, 4,4 " diamido-para-terpheny composition, can obtain and have good toughness, the film that stress is low.

In addition, above-mentioned two amine components also can replace through hydroxyl.This kind of two amino-phenol compositions for example can be enumerated: 3,3 '-dihydroxybiphenyl amine component, 3,3 '-diamido-4,4 '-dihydroxybiphenyl composition, 4,4 '-diamido-3,3 '-dihydroxybiphenyl composition, 3,3 '-diamido-4,4 '-dihydroxy-diphenyl sulfone composition, 4,4 '-diamido-3,3 '-dihydroxy-diphenyl sulfone composition, two-(3-amino-4-hydroxylphenyl) methane composition, 2,2-pair-(3-amino-4-hydroxylphenyl) propane composition, 2,2-pair-(3-amino-4-hydroxylphenyl) HFC-236fa composition, 2,2-pair-(4-amino-3-hydroxy base) HFC-236fa composition, two-(4-amino-3-hydroxy base) methane composition, 2,2-pair-(4-amino-3-hydroxy base) propane composition, 4,4 '-diamido-3,3 '-dihydroxy benaophenonel composition, 3,3 '-diamido-4,4 '-dihydroxy benaophenonel composition, 4,4 '-diamido-3,3 '-dihydroxydiphenyl ether composition, 3,3 '-diamido-4,4 '-dihydroxydiphenyl ether composition, Isosorbide-5-Nitrae-diamido-2,5-dihydroxy benzenes composition, 1,3-diamido-2,4-dihydroxy benzenes composition, 1,3-diamido-4,6-dihydroxy benzenes becomes to grade.These pair of amino-phenol composition also can be used alone or as a mixture.

In these pair of amino-phenol structure, particularly preferred aspect can be enumerated the R in above-mentioned general formula (1) ²for being selected from the situation of the bivalent radical that contains aromatic series base in following base.

[changing 8]

In above-mentioned formula, X ₁expression-O-,-S-,-C (CF ₃) ₂-,-CH ₂-,-SO ₂-,-NHCO-.* represent with above-mentioned general formula (1) in be binding on R ²-NH-or-the bond position of OH.In addition, in said structure, be binding on R ²-NH-and-OH be each other bond at ortho position (contiguous bits).

With respect to all repetitives that form resin (a), with R ²for having the content of 2 amino aromatic diamine compositions in resin (a), core is preferably 5mol%～40mol%, more preferably 10mol%～30mol%.

In addition, in order to improve the adherence with substrate, can be using silicon two amine components as with R ²two amine components for core.Its example can be enumerated: two (4-aminophenyl) dimethylsilane composition, two (4-aminophenyl) tetramethyl silica alkane composition, two (4-aminophenyl) tetramethyl disiloxane composition, two (gamma-amino propyl group) tetramethyl disiloxane composition, Isosorbide-5-Nitrae-bis-(gamma-amino propyl-dimethyl silylation) benzene composition, two (4-aminobutyl) tetramethyl disiloxane composition, two (gamma-amino propyl group) tetraphenyl disiloxane become to grade.

Silicon two amine components also can be enumerated following structure.

[changing 9]

In above-mentioned formula, R ₅and R ₆represent divalent organic base, R ₇and R ₈represent any monovalent organic radical.A plurality of R ₇can be mutually the same also can be different.A plurality of R ₈can be mutually the same also can be different.

R ₅and R ₆it is 1～20 straight chain or the alkylidene of branch, the phenylene that carbon number is 6～20, the divalence alicyclic group that carbon number is 3～20 or the base that these bases combinations are formed that represented divalent organic base represents to have substituent carbon number.

R ₇and R ₈it is 1～20 straight chain or the alkyl of branch or the aryl that carbon number is 6～20 that represented any monovalent organic radical represents to have substituent carbon number.

More specifically can enumerate following base.

[changing 10]

With respect to all repetitives that form resin (a), with R ²for having the content of at least 2 amino silicon two amine components in resin (a), core is preferably 5mol%～40mol%, more preferably 10mol%～30mol%.

While making polyimide with regard to carrying out thermmohardening, improve rectilinearity and outspoken nature, realize low stress and prevent the viewpoint of chip warpage, the viewpoint of the adherence of raising and substrate, improve the deliquescent viewpoint of alkali after exposure etc., the resin (a) with the represented repetitive of above-mentioned general formula (1) is preferably the resin with the represented repetitive of following general formula (2) and the represented repetitive of following general formula (3).

[changing 11]

In above-mentioned general formula (2),

R ¹' with above-mentioned general formula (1) in R ¹for identical meanings.

R ³' with above-mentioned general formula (1) in R ³for identical meanings.

Wherein, a plurality of-CO ₂r ' ³in there is to decompose the base that produces alkali-soluble base for effect by sour at least one.

R ⁴for containing the divalent organic base of alicyclic group.

In above-mentioned general formula (3),

R ¹" with the R in above-mentioned general formula (1) ¹for identical meanings.

R ³" with the R in above-mentioned general formula (1) ³for identical meanings.

Wherein, a plurality of-CO ₂r ³" in there is to decompose the base that produces alkali-soluble base for effect by sour at least one.

R ⁵for with R ⁴different divalent organic bases.

About R ⁴concrete example, the preference of the divalent organic base that contains alicyclic group can enumerate with about R ²the identical person of concrete example, preference of the bivalent radical that contains alicyclic group.

With R ⁴different divalent organic base R ⁵can enumerate above about R ²and the already described bivalent radical that contains aromatic series base, the bivalent radical etc. that contains silicon atom.

While making polyimide with regard to carrying out thermmohardening, improve rectilinearity and outspoken nature, realize low stress and prevent the viewpoint of chip warpage, and improve stable on heating viewpoint, the R in above-mentioned general formula (3) ⁵be preferably the bivalent radical that contains aromatic series base, about R ⁵concrete example, the preference of the bivalent radical that contains aromatic series base can enumerate with about R ²the identical person of concrete example, preference of the bivalent radical that contains aromatic series base.Any represented bivalent radical of following formula more preferably.

[changing 12]

In above-mentioned formula, the hydrogen atom of each aromatic rings can be respectively independently at least one atom or the base in selecting the cohort that free fluorine atom, chlorine atom, bromine atoms, methyl, methoxyl, cyano group, phenyl, trifluoromethyl form replace.

R ³, R ³' or R ³" the example of organic group to be preferably carbon number be 1～20, specifically can enumerate: by sour effect, base, alkyl, naphthenic base, aryl, aralkyl, thiazolinyl, alkynyl, alkoxy, the base of silicon atoms ,-CORc (Rc is alkyl, aryl, naphthenic base) ,-SO that produces alkali-soluble base occurs to decompose ₂rd (Rd is alkyl, aryl, naphthenic base, o-quinone diazido) or base that these bases are combined etc.

R ³, R ³' or R ³" represented alkyl also can have substituting group, is preferably carbon number and is 1～20 straight chain or branch's alkyl, also can in alkyl chain, contain oxygen atom, sulphur atom, nitrogen-atoms.Specifically can enumerate: the straight chained alkyls such as methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-octyl, dodecyl, n-tetradecane base, n-octadecane base, branch's alkyl such as isopropyl, isobutyl, tributyl, neopentyl, 2-ethylhexyl.Substituting group for example can be enumerated cyano group, halogen atom, hydroxyl, alkoxy, carboxyl, alkoxy carbonyl.

R ³, R ³' or R ³" represented naphthenic base also can have substituting group, is preferably carbon number and is 3～20 naphthenic base, also can be many rings, also can contain oxygen atom at ring.Specifically can enumerate: cyclopropyl, cyclopentyl, cyclohexyl, norborny, adamantyl etc.

R ³, R ³' or R ³" represented aryl also can have substituting group, is preferably carbon number and is 6～14 aryl, such as enumerating phenyl, naphthyl, anthryl etc.

R ³, R ³' or R ³" represented aralkyl also can have substituting group, preferably can enumerate carbon number and be 7～20 aralkyl, for example, can enumerate benzyl, phenethyl, naphthyl methyl, naphthyl ethyl.

R ³, R ³' or R ³" represented alkoxy also can have substituting group, is preferably carbon number and is 1～20 alkoxy, such as enumerating: methoxyl, ethoxy, propoxyl group, n-butoxy, amoxy, own oxygen base, heptan oxygen base etc.

R ³, R ³' or R ³as long as " base of represented silicon atoms contains silicon, and there is no particular restriction, is preferably silicon alkoxy (trimethyl silicane alcoxyl base, triethyl silicane oxygen base, tributyl dimethyl-silicon alcoxyl base).

R ³, R ³' or R ³" optional position that represented thiazolinyl can be set forth in the base of abovementioned alkyl, naphthenic base, aryl, aralkyl, alkoxy, silicon atoms has the base of two keys.Being preferably carbon number is 1～12, and more preferably carbon number is 1～6.For example be preferably vinyl, allyl.

R ³, R ³' or R ³" optional position that represented alkynyl can be set forth in the base of abovementioned alkyl, naphthenic base, aryl, aralkyl, alkoxy, silicon atoms has the base of triple bond.Being preferably carbon number is 1～12, and more preferably carbon number is 1～6.For example be preferably ethinyl, propargyl.

In the present invention, be present in resin (a) a plurality of-CO ₂r ³in there is to decompose the base that produces alkali-soluble base for effect by sour at least one.In above-mentioned general formula (2)-CO ₂r ³', in above-mentioned general formula (3)-CO ₂r ³" also identical.

The so-called base that produces alkali-soluble base by sour effect generation decomposition, refers to by sour effect and decomposes, the base (below also referred to as sour decomposability base) of the alkali-soluble base as resin side generation hydroxyl, carboxyl.In the present invention, sour decomposability base is preferably by sour effect and decomposes, and in resin side, produces carboxyl as the base of alkali-soluble base.

As sour decomposability base and preferred base is the base that the base to depart from because of acid forms the hydrogen atom replacement of these alkali-soluble bases.

Because the base that acid departs from for example can be enumerated :-C (R ₃₆) (R ₃₇) (R ₃₈) ,-C (R ₃₆) (R ₃₇) (OR ₃₉) ,-C (R ₀₁) (R ₀₂) (OR ₃₉) etc.In formula, R ₃₆～R ₃₉independently represent respectively alkyl, naphthenic base, aryl, aralkyl or thiazolinyl.R ₃₆with R ₃₇also bond and form ring mutually.

R ₀₁and R ₀₂independently represent respectively hydrogen atom, alkyl, naphthenic base, aryl, aralkyl or thiazolinyl.

Acid decomposability base is preferably three grades of alkyl ester groups, acetal ester group, cumyl ester group, enol ester group etc.More preferably three grades of alkyl ester groups, acetal ester group, by using this acid decomposability base, can obtain high sensitivity and high-resolution light-sensitive surface.

The hydrogen atom that is preferably carboxyl as three grades of alkyl ester groups of sour decomposability base replaces through the represented base of following general formula (AI) ester group forming.

[changing 13]

In above-mentioned general formula (AI),

T represent singly-bound or-Rt-COO-base.Rt represents alkylidene or cycloalkylidene.

Rx ₁～Rx ₃independent alkyl (straight chain or branch) or the naphthenic base (monocycle or encircle) of representing respectively more.

Rx ₁～Rx ₃two also can bond and form naphthenic base (monocycle or encircle) more.

It is 1～5 alkylidene that Rt is preferably carbon number, more preferably-CH ₂-Ji ,-(CH ₂) ₂-Ji ,-(CH ₂) ₃-Ji.

Rx ₁～Rx ₃alkyl be preferably the base that the carbon numbers such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, tributyl are 1～4.

Rx ₁～Rx ₃naphthenic base be preferably the naphthenic base of the monocycles such as cyclopentyl, cyclohexyl, the naphthenic base of many rings such as norborny, Fourth Ring decyl, Fourth Ring dodecyl, adamantyl.

Rx ₁～Rx ₃two bonds and the naphthenic base that forms is preferably the naphthenic base of the monocycles such as cyclopentyl, cyclohexyl, the naphthenic base of many rings such as norborny, Fourth Ring decyl, Fourth Ring dodecyl, adamantyl.Be particularly preferably carbon number and be the naphthenic base of 5 or 6 monocycle.

Be preferably Rx ₁for methyl or ethyl, Rx ₂with Rx ₃bond and form the aspect of above-mentioned naphthenic base.

Above-mentioned each base also can have substituting group, and substituting group is such as enumerating alkyl (carbon number is 1～4), halogen atom, hydroxyl, alkoxy (carbon number is 1～4), carboxyl, alkoxy carbonyl (carbon number is 2～6) etc., and being preferably carbon number is below 8.

Using form as the particular instantiation of the represented base of the above-mentioned general formula (AI) of three grades of alkyl ester groups of sour decomposability base in below, but the present invention is not limited to this.

In concrete example, Rxa, Rxb represent that respectively carbon number is 1～4 alkyl.Z represents the substituting group that above-mentioned each base can have, independent respectively while there is a plurality of situations.P represents 0 or positive integer.

[changing 14]

[changing 15]

As three grades of alkyl ester groups of sour decomposability base more preferably have the represented base of following general formula (I) and the represented base of following general formula (II) at least any as three grades of alkyl ester groups of the represented base of above-mentioned general formula (AI).

[changing 16]

In formula (I) and formula (II),

R ₂, R ₄, R ₅, R ₆independently represent respectively alkyl or cycloalkyl.

R represents to form the necessary atomic group of alicyclic structure together with carbon atom.

R ₂alkyl can be straight chain type and also can be branching type, also can there is substituting group.

R ₂naphthenic base can be monocycle and also can be many rings, also can there is substituting group.

R ₂be preferably alkyl, more preferably carbon number is 1～10, and then to be preferably carbon number be 1～5, for example, can enumerate methyl, ethyl.

R represents to form the necessary atomic group of alicyclic structure together with carbon atom.The formed alicyclic structure of R is preferably the alicyclic structure of monocycle, and its carbon number is for being preferably 3～7, and more preferably 5 or 6.

R ₄, R ₅, R ₆alkyl can be straight chain type and also can be branching type, also can there is substituting group.Alkyl is preferably the base that the carbon numbers such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, tributyl are 1～4.

R ₄, R ₅, R ₆naphthenic base can be monocycle and also can be many rings, also can there is substituting group.Naphthenic base is preferably the naphthenic base of the monocycles such as cyclopentyl, cyclohexyl, the naphthenic base of many rings such as norborny, Fourth Ring decyl, Fourth Ring dodecyl, adamantyl.

By the represented base of general formula (I), for example can be enumerated by following general formula (I-a) and the represented base of general formula (I-b).

[changing 17]

In formula, R ₂with the R in general formula (I) ₂for identical meanings.

The represented base of general formula (II) is preferably the represented base of following general formula (II-a).

[changing 18]

In formula (II-a),

R ₄and R ₅middle person is identical meanings with general formula (II).

The hydrogen atom that is particularly preferably carboxyl as the acetal ester group of sour decomposability base replaces through the represented base of following general formula (III) ester group forming.

[changing 19]

Ra represents hydrogen atom, alkyl, naphthenic base, aryl or aralkyl.

Rb represents singly-bound or bivalence linking base.

Q represents alkyl, can contain heteroatomic alicyclic group, maybe can contain heteroatomic fragrant cyclic group.

Ra, Rb and Q at least two also bonds and form ring mutually.This ring is preferably 5 Yuans rings or 6 Yuans rings.

As alkyl, naphthenic base, the aryl or aralkyl of Ra can enumerate with above as about the R in general formula (I) ³alkyl, naphthenic base, aryl, aralkyl and the identical base of already described person.

Ra is particularly preferably hydrogen atom, methyl, phenyl, benzyl, can obtain the light-sensitive surface of excellent sensitivity.

With regard to the decomposition of the acetal ester group of the conduct acid decomposability base in can suppressing by steric hindrance (steric hindrance) to preserve, prevent that with regard to the viewpoint of reduction of pattern voltinism, Ra is also preferably following general formula (IV) or the represented base of general formula (V).

[changing 20]

In above-mentioned general formula, Rc, Rd, Re, Rf and Rg be independent alkyl, naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkoxy carbonyl, aryloxycarbonyl, cyano group or the halogen atom of representing respectively, Rc, Rd be bond and form ring mutually also, Re, Rf and Rg at least two also bonds and form ring mutually.

If Ra is general formula (IV) or the represented base of general formula (V), can in thering is the resin of the represented repetitive of general formula (1), suppress the carrying out of the imidization reaction in preserving, prevent the reduction of pattern voltinism.

As alkyl, naphthenic base, aryl, aralkyl or the alkoxy of Rc, Rd, Re, Rf, Rg can enumerate with above as about the R in general formula (1) ³alkyl, naphthenic base, aryl, aralkyl, alkoxy and the identical base of already described person.

As the aryloxy group of Rc, Rd, Re, Rf, Rg, being preferably carbon number is 6～10 aryloxy group, specifically can enumerate phenoxy group, toloxyl, 1-naphthoxy etc.

As the alkoxy carbonyl of Rc, Rd, Re, Rf, Rg, being preferably carbon number is 1～10 alkoxy carbonyl, specifically can enumerate methoxycarbonyl, ethoxy carbonyl, straight chain or branch's propoxycarbonyl, cyclopentyloxy carbonyl, cyclohexyloxy carbonyl etc.

Aryloxy group part as the aryloxycarbonyl of Rc, Rd, Re, Rf, Rg can be enumerated the base identical with above-mentioned aryloxy group.

With regard to the decomposition of the acetal ester group of the conduct acid decomposability base in can suppressing to preserve, prevent with regard to the viewpoint of reduction of pattern voltinism, at least one that is preferably Rc, Rd in above-mentioned general formula (IV) is naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkoxy carbonyl, aryloxycarbonyl, cyano group or halogen atom, and more preferably at least one is aryl.

As the bivalence linking base of Rb for example for alkylidene (is preferably carbon number and is 1～8 alkylidene, for example methylene, ethylidene, propylidene, butylidene, hexylidene or Ya Xinji), cycloalkylidene (being preferably carbon number and being 3～15 cycloalkylidene, for example cyclopentylene or cyclohexylidene) ,-S-,-O-,-CO-,-CS-,-SO ₂-,-N (R ₀)-or these two or more combination, preferably total carbon number is 20 following persons.Herein, R ₀for example, for hydrogen atom or alkyl (alkyl that carbon number is 1～8 is particularly methyl, ethyl, propyl group, normal-butyl, the second butyl, hexyl and octyl group etc.).

Rb be preferably singly-bound, alkylidene or comprise alkylidene with-O-,-CO-,-CS-and-N (R ₀)-at least one the bivalence linking base of combination, more preferably singly-bound, alkylidene or the bivalence linking base that comprises alkylidene and the combination of-O-.Herein, R ₀with above-mentioned R ₀for identical meanings.

Alkyl as Q is for example identical with the alkyl as above-mentioned Ra.

Alicyclic group and fragrant cyclic group as Q for example can be enumerated naphthenic base and the aryl as above-mentioned Ra.Its carbon number is preferably 3～18.For example, moreover in the present invention, the base a plurality of aromatic rings being linked via singly-bound (xenyl, terphenyl) is also included within the aromatic series base of Q.

Contain heteroatomic alicyclic group and contain heteroatomic fragrant cyclic group and for example can enumerate: thiirane (thiirane), ring thiacyclopentane (cyclothiolane), thiophene, furans, pyrroles, benzothiophene, coumarone, benzopyrrole, triazine, imidazoles, benzimidazole, triazole, thiadiazoles, thiazole and pyrrolidone.

Alicyclic group and fragrant cyclic group as Q also can have substituting group, for example, can enumerate alkyl, naphthenic base, cyano group, halogen atom, hydroxyl, alkoxy, carboxyl, alkoxy carbonyl.

(Rb-Q) is particularly preferably methyl, aryloxy group ethyl, cyclohexyl ethyl or aryl ethyl, and dissolubility, thermal stability improve.

At least two mutual bonds of Ra, Rb and Q and the situation that forms ring for example can be enumerated: any of Rb and Q and Ra bond and form propylidene or butylidene, form 5 Yuans rings containing oxygen atom or the situation of 6 Yuans rings.

If the summation of the carbon number of Ra, Rb and Q is denoted as to N _c, at N _cduring large situation, the alkali dissolution velocity of the resin (a) before and after the represented base of general formula (III) departs from changes and becomes greatly, dissolves that contrast uprises and resolution raising.N _cscope be preferably 2～20, be particularly preferably 2～15.If N _cbe below 20, the glass transition temperature that can suppress macromolecular compound reduces, and then can suppress to be attached to from the disengaging thing of sour decomposability base the generation of the defect on pattern.

At least one that is preferably Ra, Rb and Q is electrophilic base or the base that contains electrophilic base.Thus, in thering is the resin (a) of the represented repetitive of above-mentioned general formula (1), the decomposition of the sour decomposability base in preserving can be suppressed, the reduction of pattern voltinism can be prevented.

Electrophilic base is such as enumerating: alkoxy, aryl, thiazolinyl, alkynyl, halogen atom, acyl group, aryl carbonyl, alkoxy carbonyl, aryloxycarbonyl, aryloxy group, itrile group (cyano group), alkyl sulphonyl, aryl sulfonyl, nitro etc., be preferably alkoxy, aryl, acyl group.

Below, formation is shown as the concrete example of the represented base of the above-mentioned general formula (III) of the acetal ester group of sour decomposability base, but is not limited to these concrete examples.

[changing 21]

[changing 22]

[changing 23]

In above-mentioned general formula (1)-CO ₂r ³, in above-mentioned general formula (2)-CO ₂r ³' or above-mentioned general formula (3) in-CO ₂r ³" heat decomposition temperature be preferably 100 ℃～220 ℃, more preferably 120 ℃～210 ℃, be particularly preferably 140 ℃～200 ℃.Heat decomposition temperature for example can be analyzed and be obtained by differential thermobalance.

If heat decomposition temperature is too low, the storage stability of photosensitive polymer combination of the present invention may reduce.If heat decomposition temperature is too high, there is stress to become anxiety large and that chip warpage change is large.In addition, there is remaining analyte in film, become the former therefore anxiety that ease gas or reliability reduce.

By heat decomposition temperature being set as to 100 ℃～220 ℃, the stress of sclerosis relief pattern of the present invention becomes lower, and it is less that chip warpage becomes.Though the reason that stress becomes lower is uncertain, can infer, by heat decomposition temperature being set as to 100 ℃～220 ℃, in the represented repetitive of general formula (1)-CO ₂r ³when low-temperature setting, become-CO ₂h and carry out acid imide closed loop, improves regiospecific in the face of polyimide film, stress step-down thus.

Can realize the R of heat decomposition temperature as above ³, R ³' or R ³" structure specifically can enumerate:

Rx in above-mentioned general formula (A1) ₁～Rx ₃in at least one be the represented base of following general formula (VI) structure,

Ra in above-mentioned general formula (III) is the structure of the represented base of above-mentioned general formula (IV) or following general formula (VII) etc.

[changing 23]

In above-mentioned general formula (VI),

R ₇～R ₈independent hydrogen atom, alkyl (straight chain or branch) or naphthenic base (monocycle or encircle), the R of representing respectively more ₇～R ₈at least one be hydrogen atom.

[changing 23]

In above-mentioned general formula (VII),

Rh represents alkyl, naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkoxy carbonyl, aryloxycarbonyl, cyano group or halogen atom.

About R ₇～R ₈alkyl, the concrete example of naphthenic base, preference can be enumerated with above as about Rx ₁～Rx ₃alkyl, naphthenic base and the already described identical person of concrete example, preference.

As alkyl, naphthenic base, aryl, aralkyl or the alkoxy of Rh can enumerate with above as about the R in general formula (1) ³alkyl, naphthenic base, aryl, aralkyl, alkoxy and the identical base of already described person.

As the aryloxy group of Rh, being preferably carbon number is 6～10 aryloxy group, specifically can enumerate phenoxy group, toloxyl, 1-naphthoxy etc.

As the alkoxy carbonyl of Rh, being preferably carbon number is 1～10 alkoxy carbonyl, specifically can enumerate methoxycarbonyl, ethoxy carbonyl, straight chain or branch's propoxycarbonyl, cyclopentyloxy carbonyl, cyclohexyloxy carbonyl etc.

Aryloxy group part as the aryloxycarbonyl of Rh can be enumerated person identical with above-mentioned aryloxy group.

In the present invention, can be at R ³in make hydrogen atom mix existence with organic group.Be preferably with respect to all R in resin (a) ³and be respectively 100mol%～20mol%, more preferably 100mol%～40mol% is organic group.By adjusting this R ³hydrogen atom and the amount of organic group, the dissolution velocity of aqueous alkali is changed, therefore can obtain the photosensitive polymer combination with appropriate dissolution velocity by this adjustment.

Own-CO in resin (a) ₂r ³in, by sour effect, there is to decompose shared ratio, the so-called protection ratio of base that produces alkali-soluble base and be preferably 40%～100%, more preferably 45%～100%.

In addition, in the present invention, can make end-capping reagent and using the end reaction of the represented structural unit of general formula (1) as the polymkeric substance of major component.End-capping reagent can be used monoamine, acid anhydrides, monocarboxylic acid, single chloride compounds, single active ester compound etc.By end-capping reagent is reacted, can be by the repeat number of structural unit, be that molecular weight is controlled in preferable range, with regard in this respect preferably.And then, can suppress by the sour inactivation due to terminal amine and acidic neutralization by end-capping reagent.In addition, the cross-linking reaction base that by making end-capping reagent and end reaction, can import various organic groups, for example has carbon-to-carbon unsaturated bond is as terminal groups.

Monoamine for end-capping reagent can be enumerated: 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxyl-8-amino naphthalenes, 1-hydroxyl-7-amino naphthalenes, 1-hydroxyl-6-amino naphthalenes, 1-hydroxyl-5-amino naphthalenes, 1-hydroxyl-4-amino naphthalenes, 1-hydroxyl-3-amino naphthalenes, 1-hydroxyl-2-amino naphthalenes, 1-amino-7-hydroxyl naphthalene, 2-hydroxyl-7-amino naphthalenes, 2-hydroxyl-6-amino naphthalenes, 2-hydroxyl-5-amino naphthalenes, 2-hydroxyl-4-amino naphthalenes, 2-hydroxyl-3-amino naphthalenes, 1-amino-2 hydroxy naphthalene, 1-carboxyl-8-amino naphthalenes, 1-carboxyl-7-amino naphthalenes, 1-carboxyl-6-amino naphthalenes, 1-carboxyl-5-amino naphthalenes, 1-carboxyl-4-amino naphthalenes, 1-carboxyl-3-amino naphthalenes, 1-carboxyl-2-amino naphthalenes, 1-amino-7-carboxyl naphthalene, 2-carboxyl-7-amino naphthalenes, 2-carboxyl-6-amino naphthalenes, 2-carboxyl-5-amino naphthalenes, 2-carboxyl-4-amino naphthalenes, 2-carboxyl-3-amino naphthalenes, 1-amino-2-carboxyl naphthalene, the amino niacin of 2-, the amino niacin of 4-, the amino niacin of 5-, the amino niacin of 6-, 4-ASA, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-O-toluic acid, ammelide (ammelide), 2-aminobenzoic acid, 3-aminobenzoic acid, PABA, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxy-pyrimidine, Ortho-Aminophenol, 3-amino-phenol, PAP, 5-amino-thiooxine, 4-amino-thiooxine, 1-sulfydryl-8-amino naphthalenes, 1-sulfydryl-7-amino naphthalenes, 1-sulfydryl-6-amino naphthalenes, 1-sulfydryl-5-amino naphthalenes, 1-sulfydryl-4-amino naphthalenes, 1-sulfydryl-3-amino naphthalenes, 1-sulfydryl-2-amino naphthalenes, 1-amino-7-mercaptonaphthalene, 2-sulfydryl-7-amino naphthalenes, 2-sulfydryl-6-amino naphthalenes, 2-sulfydryl-5-amino naphthalenes, 2-sulfydryl-4-amino naphthalenes, 2-sulfydryl-3-amino naphthalenes, 1-amino-2-mercapto phenyl formic naphthalene, 3-amino-4,6-dimercapto pyrimidine, 2-amino thiophenol, 3-amino thiophenol, 4-amino thiophenol, 2-acetylenylaniline, 3-acetylenylaniline, 4-acetylenylaniline, 2,4-diacetylene aniline, 2,5-diacetylene aniline, 2,6-diacetylene aniline, 3,4-diacetylene aniline, 3,5-diacetylene aniline, 1-ethinyl-2-amino naphthalenes, 1-ethinyl-3-amino naphthalenes, 1-ethinyl-4-amino naphthalenes, 1-ethinyl-5-amino naphthalenes, 1-ethinyl-6-amino naphthalenes, 1-ethinyl-7-amino naphthalenes, 1-ethinyl-8-amino naphthalenes, 2-ethinyl-1-amino naphthalenes, 2-ethinyl-3-amino naphthalenes, 2-ethinyl-4-amino naphthalenes, 2-ethinyl-5-amino naphthalenes, 2-ethinyl-6-amino naphthalenes, 2-ethinyl-7-amino naphthalenes, 2-ethinyl-8-amino naphthalenes, 3,5-diacetylene-1-amino naphthalenes, 3,5-diacetylene-2-amino naphthalenes, 3,6-diacetylene-1-amino naphthalenes, 3,6-diacetylene-2-amino naphthalenes, 3,7-diacetylene-1-amino naphthalenes, 3,7-diacetylene-2-amino naphthalenes, 4,8-diacetylene-1-amino naphthalenes, 4,8-diacetylene-2-amino naphthalenes etc., but be not limited to these compounds.

In these compounds, be preferably 5-amino-8-hydroxyquinoline, 1-hydroxyl-7-amino naphthalenes, 1-hydroxyl-6-amino naphthalenes, 1-hydroxyl-5-amino naphthalenes, 1-hydroxyl-4-amino naphthalenes, 2-hydroxyl-7-amino naphthalenes, 2-hydroxyl-6-amino naphthalenes, 2-hydroxyl-5-amino naphthalenes, 1-carboxyl-7-amino naphthalenes, 1-carboxyl-6-amino naphthalenes, 1-carboxyl-5-amino naphthalenes, 2-carboxyl-7-amino naphthalenes, 2-carboxyl-6-amino naphthalenes, 2-carboxyl-5-amino naphthalenes, 2-aminobenzoic acid, 3-aminobenzoic acid, PABA, 4-ASA, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxy-pyrimidine, Ortho-Aminophenol, 3-amino-phenol, PAP, 2-amino thiophenol, 3-amino thiophenol, 4-amino thiophenol, 3-acetylenylaniline, 4-acetylenylaniline, 3, 4-diacetylene aniline, 3, 5-diacetylene aniline etc.

Acid anhydrides, monocarboxylic acid, single chloride compounds, active ester compound as end-capping reagent can be enumerated: the acid anhydrides such as phthalic anhydride, maleic anhydride, resistance to ground acid anhydrides, cyclohexane dicarboxylic acid acid anhydride, 3-hydroxyl phthalic anhydride, 2-carboxylic phenol, 3-carboxylic phenol, 4-carboxylic phenol, 2-carboxyl thiophenol, 3-carboxyl thiophenol, 4-carboxyl thiophenol, 1-hydroxyl-8-carboxyl naphthalene, 1-hydroxyl-7-carboxyl naphthalene, 1-hydroxyl-6-carboxyl naphthalene, 1-hydroxyl-5-carboxyl naphthalene, 1-hydroxyl-4-carboxyl naphthalene, 1-hydroxyl-3-carboxyl naphthalene, 1-hydroxyl-2-carboxyl naphthalene, 1-sulfydryl-8-carboxyl naphthalene, 1-sulfydryl-7-carboxyl naphthalene, 1-sulfydryl-6-carboxyl naphthalene, 1-sulfydryl-5-carboxyl naphthalene, 1-sulfydryl-4-carboxyl naphthalene, 1-sulfydryl-3-carboxyl naphthalene, 1-sulfydryl-2-carboxyl naphthalene, 2-carboxyl benzene sulfonic acid, 3-carboxyl benzene sulfonic acid, 4-carboxyl benzene sulfonic acid, 2-acetylenylbenzene formic acid, 3-acetylenylbenzene formic acid, 4-acetylenylbenzene formic acid, 2,4-diacetylene benzoic acid, 2,5-diacetylene benzoic acid, 2,6-diacetylene benzoic acid, 3,4-diacetylene benzoic acid, 3,5-diacetylene benzoic acid, 2-ethinyl-1-naphthoic acid, 3-ethinyl-1-naphthoic acid, 4-ethinyl-1-naphthoic acid, 5-ethinyl-1-naphthoic acid, 6-ethinyl-1-naphthoic acid, 7-ethinyl-1-naphthoic acid, 8-ethinyl-1-naphthoic acid, 2-ethinyl-2-naphthoic acid, 3-ethinyl-2-naphthoic acid, 4-ethinyl-2-naphthoic acid, 5-ethinyl-2-naphthoic acid, 6-ethinyl-2-naphthoic acid, 7-ethinyl-2-naphthoic acid, single chloride compounds that the carboxyl of the monocarboxylic acid classes such as 8-ethinyl-2-naphthoic acid and these monocarboxylic acids forms through chloride, and terephthalic acid (TPA), phthalic acid, maleic acid, cyclohexane dicarboxylic acid, 3-hydroxyl phthalic, 5-norborene-2,3-dicarboxylic acid, 1,2-dicarboxyl naphthalene, 1,3-dicarboxyl naphthalene, 1,4-dicarboxyl naphthalene, 1,5-dicarboxyl naphthalene, 1,6-dicarboxyl naphthalene, 1,7-dicarboxyl naphthalene, 1,8-dicarboxyl naphthalene, 2,3-dicarboxyl naphthalene, 2,6-dicarboxyl naphthalene, 2, the only single chloride compounds that carboxyl forms through chloride of the omega-dicarboxylic acids such as 7-dicarboxyl naphthalene, by single chloride compounds and N-hydroxybenzotriazole or N-hydroxyl-5-norborene-2, the imido reaction of 3-dicarboxyl and active ester compound of obtaining etc.

In these compounds, be preferably phthalic anhydride, maleic anhydride, resistance to ground acid anhydrides, cyclohexane dicarboxylic acid acid anhydride, the acid anhydrides such as 3-hydroxyl phthalic anhydride, 3-carboxylic phenol, 4-carboxylic phenol, 3-carboxyl thiophenol, 4-carboxyl thiophenol, 1-hydroxyl-7-carboxyl naphthalene, 1-hydroxyl-6-carboxyl naphthalene, 1-hydroxyl-5-carboxyl naphthalene, 1-sulfydryl-7-carboxyl naphthalene, 1-sulfydryl-6-carboxyl naphthalene, 1-sulfydryl-5-carboxyl naphthalene, 3-carboxyl benzene sulfonic acid, 4-carboxyl benzene sulfonic acid, 3-acetylenylbenzene formic acid, 4-acetylenylbenzene formic acid, 3,4-diacetylene benzoic acid, the monocarboxylic acid classes such as 3,5-diacetylene benzoic acid, and single chloride compounds of forming through chloride of the carboxyl of these monocarboxylic acids, terephthalic acid (TPA), phthalic acid, maleic acid, cyclohexane dicarboxylic acid, 1,5-dicarboxyl naphthalene, 1,6-dicarboxyl naphthalene, 1,7-dicarboxyl naphthalene, the only single chloride compounds that carboxyl forms through chloride of the omega-dicarboxylic acids such as 2,6-dicarboxyl naphthalene, by single chloride compounds and N-hydroxybenzotriazole or N-hydroxyl-5-norborene-2, the imido reaction of 3-dicarboxyl and active ester compound of obtaining etc.

With respect to all amine components, for the importing ratio of the monoamine of end-capping reagent, be preferably the scope of 0.1mol%～60mol%, be particularly preferably 5mol%～50mol%.With respect to two amine components, as the importing ratio that is selected from the compound in acid anhydrides, monocarboxylic acid, single chloride compounds and single active ester compound of end-capping reagent, be preferably the scope of 0.1mol%～100mol%, be particularly preferably 5mol%～90mol%.By multiple end-capping reagent is reacted, can import a plurality of different terminal groups.

The end-capping reagent importing in polymkeric substance can utilize following method easily to detect.For example importing is had to the polymer dissolution of end-capping reagent in acid solution, resolve into amine component and acid anhydrides composition as the structural unit of polymkeric substance.It is carried out to gas chromatography (Gas Chromatography, GC) or nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) mensuration, can easily detect end-capping reagent thus.In addition, by importing, have the component of polymer of end-capping reagent directly carry out pyrolysis gas chromatography (Pyro-GC) (Pyrolysis Gas Chromatography, PGC) or infrared spectrum and ¹³cNMR spectroscopic assay, also can easily detect.

In photosensitive polymer combination of the present invention, resin (a) used is preferably and usings the represented structural unit of general formula (1) as major component.So-called major component, refers to the represented structural unit of general formula (1) containing more than 70mol% herein.More preferably more than 80mol%, more than most preferably being 90mol%.

In the present invention, resin used also can be the represented structural unit of general formula (1) and the multipolymer of other structural units, or also can be the potpourri of the various kinds of resin that contains the represented structural unit of general formula (1).

And then, also can be the resin that contains the represented structural unit of general formula (1) with not for example, containing the resin of the represented structural unit of general formula (1) (R in general formula (1) ²be only the resin of aromatic rings) potpourri.When this situation, be preferably the resin that contains the represented structural unit of general formula (1) containing more than 50 quality %, more than more preferably containing 75 quality %.

For the kind of the structural unit of copolymerization or mixing and quantity, be preferably in the stable on heating scope that does not undermine finally the polymkeric substance by heat treated gained and select.

With regard to the viewpoint of alkali dissolution velocity, film physical property etc., the resin (a) that contains the represented repetitive of above-mentioned general formula (1) is preferably below 200,000 in quality mean molecular weight, and more preferably 1,000～200,000, and then be preferably 2,000～100,000, be particularly preferably 3,000～100,000.By being set as this molecular weight ranges, can obtain the light-sensitive surface of the excellent in resolution that stress is low, mechanical property is excellent and then developing defect is few.Moreover in the present invention, molecular weight can pass through gel permeation chromatography (Gel Permeation Chromatography, GPC) to be measured, and use polystyrene standard calibration curve and obtain.

Dispersion degree (molecular weight distribution) is preferably 1.0～4.0, and more preferably 1.0～3.5.

The manufacture method of the resin in the present invention (a) can use arbitrarily before known method (for example, with reference to up-to-date polyimide～basis and application～(Japanese polyimide research association volume)).

For example, when the situation of polyamic acid or poly amic acid ester, there is following methods: the method that makes tetracarboxylic dianhydride react with diamine compound in low temperature; By tetracarboxylic dianhydride and alcohol, obtain diester, the method for reacting thereafter under the existence of amine and condensation agent; By tetracarboxylic dianhydride and alcohol, obtain diester, thereafter by remaining dicarboxylic acid chloride, and the method for reacting with amine; A part to the carboxyl of side chain is carried out imidizate by thermal treatment, or uses esterifying reagent etc. to carry out the method etc. of alkyl esterification.

Wherein, with regard to the aspect of cost, ease-to-operate, performance repeatability, be preferably following methods: in organic solvent, make diamine compound at-20 ℃～50 ℃, react a few minutes with tetracarboxylic dianhydride to several days, obtain thus polyamic acid, then under alkali condition, react with halogenide class, or under acid condition, react with ethene ethers or react with the dialkyl acetal of dimethyl formamide, obtain thus the method (synthetic method 1) of the poly amic acid ester of general formula (1); In addition, as high polymer chemistry (Makromol.Chem.), the synthetic dicarboxylic acid with sour decomposability base as recording in 194,511～521 (1993), carries out the method (synthetic method 2) of polycondensation then with diamines.

(synthetic method 1)

[changing 24]

(synthetic method 2)

[changing 25]

In above-mentioned flow process, R ¹, R ²and R ³middle person is identical meanings with general formula (1).

In the synthetic reaction of this polyamic acid, spendable organic solvent can illustration: the acid amides series solvents such as DMF, DMA, METHYLPYRROLIDONE, DMI; The aromatic series series solvent of benzene, methyl phenyl ethers anisole, diphenyl ether, nitrobenzene, cyanobenzene, pyridine and so on; Chloroform, methylene chloride, 1,2-ethylene dichloride, 1,1,2, the halogen series solvent of 2-tetrachloroethane and so on; The ether series solvent of tetrahydrofuran, dioxan, diethylene glycol dimethyl ether and so on etc.Wherein be preferably acid amides series solvent, can obtain the polyamic acid of high molecular.

In polyreaction, the boiling point of organic solvent used is preferably more than 50 ℃, more preferably more than 100 ℃, is particularly preferably more than 150 ℃.

The concentration of the solute in reactant liquor is preferably 1 quality %～50 quality %, and more preferably 5 quality %～30 quality %, are particularly preferably 10 quality %～20 quality %.

The poly amic acid ester obtaining as mentioned above can be together with composition (b) on the substrate of semiconductor substrate etc. masking, then by micro-shadow step formation relief pattern.By the heat treated of this pattern, poly amic acid ester or polyamic acid generation dehydration closed-loop, obtain polyimide cured film.

In the present invention, for thering is the poly amic acid ester of the structural unit shown in above-mentioned general formula (1), by the i radiant transmittance of the thickness 20μ m unit of the formed film of this precursor, be more than 1%, be preferably more than 5%, more preferably more than 10%, be particularly preferably 10%～80%.If this value is less than 1%, be difficult to obtain resolving power high and can form the photosensitive polymer combination of the good pattern of shape.The transmissivity of i ray (light of wavelength 365nm) can be passed through spectrophotometer (for example the U3410 of Hitachi type, Hitachi (thigh) manufacture) and measure.

In addition, by the poly amic acid ester with the structural unit shown in above-mentioned general formula (1), carry out acid imide closed loop and the residual stress of the polyimide cured film that forms is preferably below 25MPa, more preferably below 20MPa.

Herein, if surpass 25MPa, the shortcoming that has the amount of warpage of silicon wafer or the residual strain of silicon inside to increase.Moreover the residual stress of polyimide film can for example, be measured at the lower membrane stress determinator (KLA-Tencor (Tencor) company manufactures, FLX-2320 type) that passes through of normal temperature (25 ℃).

Meet the poly amic acid ester of the structural unit shown in the above-mentioned general formula of having of these characteristics (1) by selecting suitable monomer to there is following structure: the pi-conjugated length of aromatic rings is inhibited, and can form upright and outspoken and linear main chain.

In addition, in the present invention, resin (a) can be used a kind of, also can be also with multiple.And then, also can and use resin (a) resin in addition.

(b) the acidic compound by the irradiation of active ray or radioactive ray

Composition of the present invention contains the acidic compound (also referred to as " light acid producing agent " or " (b) composition ") by the irradiation of active ray or radioactive ray.These compounds also can and be used two or more uses.In addition, in order to adjust sensitivity, also can and with sensitizer etc.

(b1) light acid producing agent

The irradiation of passing through active ray or radioactive ray that light acid producing agent is suitably used in the light trigger of choice for use light cationic polymerization, the light depigmenting agent of the light trigger of optical free radical polymerization, pigment, phototropic agent or micro-resist (microresist) etc. and the potpourri of acidic known compound and these compounds.

For example can enumerate: diazo salt, phosphonium salt, sulfonium salt, Iodonium salt, acid imide sulphonic acid ester, oxime sulfonates, diazonium two sulfones, two sulfones, adjacent nitrobenzyl sulfonate esters.

In addition, can use the irradiation by active ray or radioactive ray and acidic base or compound are directed into the compound forming on the main chain of polymkeric substance or side chain, for example United States Patent (USP) the 3rd, 849, No. 137, No. 3914407th, Deutsche Bundespatent, clear No. 63-26653 of Japanese Patent Laid-Open, clear No. 55-164824 of Japanese Patent Laid-Open, clear No. 62-69263 of Japanese Patent Laid-Open, clear No. 63-146038 of Japanese Patent Laid-Open, clear No. 63-163452 of Japanese Patent Laid-Open, clear No. 62-153853 of Japanese Patent Laid-Open, the compound of recording in the clear 63-146029 of Japanese Patent Laid-Open grade.

And then, also can use United States Patent (USP) the 3rd, 779, No. 778, Europe patent the 126th, that in No. 712 grades, records passes through light and acidic compound.

By the irradiation of active ray or radioactive ray, in acidic compound, preferred compound can be enumerated following general formula (ZI), general formula (ZII), the represented compound of general formula (ZIII).

[changing 26]

In above-mentioned general formula (ZI),

R ₂₀₁, R ₂₀₂and R ₂₀₃independently represent respectively organic group.

In above-mentioned general formula (ZII), general formula (ZIII),

R ₂₀₄～R ₂₀₇independently represent respectively aryl, alkyl or cycloalkyl.

X ^-represent non-nucleophilicity negative ion, preferably can enumerate azochlorosulfonate acid anion, carboxylate anion, two (alkyl sulphonyl) amide anion, three (alkyl sulphonyl) methide negative ion, BF ₄ ^-, PF ₆ ^-, SbF ₆-etc., be preferably the organic anion with carbon atom.

Preferred organic anion can be enumerated the organic anion shown in following general formula.

[changing 27]

In above-mentioned general formula,

Rc ₁represent organic group.

Rc ₁organic group can to enumerate carbon number be 1～30 base, preferably can enumerate a plurality of through singly-bound ,-O-,-CO of alkyl, naphthenic base, aryl or these bases that can be substituted ₂-,-S-,-SO ₃-,-SO ₂n (Rd ₁the base that concatenating group such as)-wait links.

Rd ₁represent hydrogen atom or alkyl.

Rc ₃, Rc ₄and Rc ₅independently represent respectively organic group.

Rc ₃, Rc ₄and Rc ₅organic group can enumerate and Rc ₁the identical person of preferred organic group, be preferably carbon number and be 1～4 perfluoroalkyl.

Rc ₃with Rc ₄also can bond and form ring.

Rc ₃with Rc ₄bond and the base that forms can be enumerated alkylidene, cycloalkylidene, arlydene.Be preferably carbon number and be 2～4 sub-perfluoroalkyl (perfluoroalkyl alkylene).

Rc ₁and Rc ₃～Rc ₅the organic group phenyl that is preferably 1 alkyl replacing through fluorine atom or fluoroalkyl, replaces through fluorine atom or fluoroalkyl.By having fluorine atom or fluoroalkyl, the sour acid degree producing by irradiation improves, and sensitivity improves.In addition, pass through Rc ₃with Rc ₄bond and form ring, the sour acid degree producing by irradiation improves, and sensitivity improves and preferably.

In general formula (ZI),

As R ₂₀₁, R ₂₀₂and R ₂₀₃the carbon number of organic group be generally 1～30, be preferably 1～20.About R ₂₀₁～R ₂₀₃organic group can enumerate aryl, alkyl, naphthenic base etc.

In addition, R ₂₀₁～R ₂₀₃in two also can bond and form ring structure, also can contain oxygen atom, sulphur atom, ester bond, amido link, carbonyl at ring.R ₂₀₁～R ₂₀₃in two bonds and the base that forms can be enumerated alkylidene (for example butylidene, pentylidene).

In above-mentioned general formula (ZII), general formula (ZIII), R ₂₀₄～R ₂₀₇aryl be preferably phenyl, naphthyl, and then be preferably phenyl.R ₂₀₄～R ₂₀₇aryl also can be the aryl with the heterocycle structure that contains oxygen atom, nitrogen-atoms, sulphur atom etc.There is the skeleton of aryl of heterocycle structure such as enumerating: pyrroles, furans, thiophene, indoles, coumarone, benzothiophene etc.

R ₂₀₄～R ₂₀₇alkyl and naphthenic base preferably can to enumerate carbon number be the naphthenic base (cyclopentyl, cyclohexyl, norborny) that 1～10 straight chain or branch's alkyl (for example methyl, ethyl, propyl group, butyl, amyl group), carbon number are 3～10.

R ₂₀₄～R ₂₀₇aryl, alkyl, naphthenic base also can there is substituting group.R ₂₀₄～R ₂₀₇aryl, alkyl, the naphthenic base substituting group that can have such as enumerating: alkyl (being 1～15 such as carbon number), naphthenic base (being 3～15 such as carbon number), aryl (being 6～15 such as carbon number), alkoxy (being 1～15 such as carbon number), halogen atom, hydroxyl, thiophenyl etc.

< triarylsulfonium salt >

Triarylsulfonium salt particularly preferably, is preferably further and uses sensitizer with regard to the aspect of thermal stability, sensitivity.

This kind of compound optionally can and be used two or more uses.

Triarylsulfonium salt is preferably at least one aryl and has electrophilic base as substituting group, and then the summation that is preferably substituent Hammett (Hammet) value that is binding on aryl skeleton is greater than 0.18.

Herein, so-called electrophilic base, refers to that Hammett value (Hammett substituent constant σ) is greater than 0 substituting group.In the present invention, with regard to the viewpoint of high-sensitivity, the summation that is preferably the substituent Hammett value that is binding on aryl skeleton in specific light acid producing agent is more than 0.18, is more preferably greater than 0.46, and then is preferably more than 0.60.

In addition, Hammett value representation has the degree of the cationic electrophilic of triarylsulfonium salt structure, with regard to the viewpoint of high-sensitivity, there is no special higher limit, but with regard to the viewpoint of reactive and stability, be preferably and surpass 0.46 and be less than 4.0, more preferably surpass 0.50 and be less than 3.5, be particularly preferably and surpass 0.60 and be less than 3.0 scope.

Moreover the Hammett value in the present invention is the numerical value of recording in chemical discussion group-10 Hammett's rule-structure and reactivity-(nineteen eighty-three ball kind (thigh) distribution) of using this Naoki of rice to compile.

The electrophilic base being directed in aryl skeleton can be enumerated: trifluoromethyl, halogen atom, ester group, sulfoxide group, cyano group, amide group, carboxyl, carbonyl etc.These substituent Hammett values are shown in following.Can enumerate: trifluoromethyl (CF ₃, m:0.43, p:0.54), halogen atom [for example-F (m:0.34, p:0.06) ,-Cl (m:0.37, p:0.23) ,-Br (m:0.39, p:0.23) ,-I (m:0.35, P:0.18)], ester group (for example-COCH ₃, o:0.37, p:0.45), sulfoxide group (for example-SOCH ₃, m:0.52, p:0.45), cyano group (CN, m:0.56, p:0.66), amide group (for example-NHCOCH ₃, m:0.21, p:0.00), carboxyl (COOH, m:0.37, p:0.45), carbonyl (CHO, m:0.36, p:(043)) etc.In parantheses, represent importing position and the Hammett value thereof of this substituting group in aryl skeleton, so-called (m:0.50), represents that Hammett value when position is upper between this substituting group is directed into is 0.50.

In these substituting groups, with regard to hydrophobic viewpoint, be preferably the substituting group of the nonionics such as halogen atom, halogenated alkyl, wherein, with regard to reactive viewpoint, be preferably-Cl, with regard to the viewpoint of hydrophobic property, be preferably-F ,-CF ₃,-Cl ,-Br.

These substituting groups can be directed in any in 3 aryl skeletons of triarylsulfonium salt structure, also can be directed on 2 above aryl skeletons.In addition, 3 aryl skeletons separately the upper substituting group importing can be one and also can be a plurality of.In the present invention, the summation that is preferably the substituent Hammett value importing on these aryl skeletons surpasses 0.18, more preferably surpasses 0.46.The substituent number importing is for any.Place that for example can be in the aryl skeleton of triarylsulfonium salt structure only imports Hammett value king-sized (for example the Hammett value of an independent base over 0.46) substituting group.In addition, for example also can import a plurality of substituting groups and the Hammett value of each imported base is added up to over 0.46.

As mentioned above, substituent Hammett value is according to the position importing and difference, and therefore the summation of the Hammett value of specific light acid producing agent of the present invention is to determine according to substituent kind, importing position, importing number.

Moreover Hammett's rule normally represents with m () position, p (to) position, in the present invention, as the index of electrophilic, the substituting group effect on adjacent (o) position is calculated to the value that work is identical with p position.About preferred the position of substitution, with regard to the viewpoint on synthetic, be preferably m position, p position, most preferably be p position.

In the present invention, be preferably the sulfonium salt replacing through more than three halogen atoms, most preferably be the sulfonium salt replacing through three chloros, particularly, be preferably have on 3 aryl skeletons import respectively have halogen atom, the triarylsulfonium salt structure person of most preferably be-Cl, more preferably-Cl is replaced on p position.

The azochlorosulfonate acid anion that the contained triarylsulfonium salt of composition of the present invention has be such as enumerating aryl sulfonic acid root negative ion, alkyl sulfonic acid root negative ion etc., is preferably through fluorine atom or has the negative ion that the organic group of fluorine atom replaces.

The compound with triarylsulfonium salt structure for example can pass through JACS (J.Am.Chem.Soc.) the 112nd volume (16), nineteen ninety; Pp.6004-6015, organic chemistry periodical (J.Org.Chem.) 1988; The method of recording in 5571-5573 page, WO02/081439A1 handbook or No. 1113005 instructions of Europe patent (EP) etc. and easily synthetic.

Below enumerate concrete example, but be not limited to these examples.

[changing 28]

[changing 29]

And then can enumerate: triphenylsulfonium fluoroform sulphonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyl diphenyl sulfonium fluoroform sulphonate, 4-methoxyphenyl diphenyl sulfonium trifluoroacetate, 4-thiophenyl phenyl diphenyl sulfonium fluoroform sulphonate or 4-thiophenyl phenyl diphenyl sulfonium trifluoroacetate etc.

Er Fang Ji Iodonium salt can be enumerated: Er Ben Ji Iodonium trifluoroacetate, Er Ben Ji Iodonium fluoroform sulphonate, 4-methoxyphenyl Ben Ji Iodonium fluoroform sulphonate, 4-methoxyphenyl Ben Ji Iodonium trifluoroacetate, phenyl, 4-(2 '-hydroxyl-1 '-tetradecyloxyaniline) Ben Ji Iodonium fluoroform sulphonate, 4-(2 '-hydroxyl-1 '-tetradecyloxyaniline) Ben Ji Iodonium hexafluoro antimonate, phenyl, 4-(2 '-hydroxyl-1 '-tetradecyloxyaniline) Ben Ji Iodonium-tosilate etc.; Diazomethane derivative can be enumerated: two (cyclohexyl sulfonyl) diazomethane, two (tributyl sulfonyl) diazomethane, two (p-toluenesulfonyl) diazomethane etc.;

Acid imide sulfonate derivatives can be enumerated: trimethyl fluoride sulfonyl oxygen base dicyclo [2.2.1] heptan-5-alkene dicarboxyl acid imide, succinimide trifluoromethane sulfonic acid ester, phthalimide p-toluenesulfonic acid ester, phthalimide trifluoromethane sulfonic acid ester, N-hydroxyl naphthalimide methanesulfonates, N-hydroxyl-5-norborene-2,3-dicarboxyl acid imide propane sulfonic acid ester etc.

In addition, by the irradiation of active ray or radioactive ray, in acidic compound, with regard to the viewpoints such as sensitivity, resolution, specific inductive capacity, dimensional stability, most preferably example can be enumerated oxime compound, more preferably can enumerate oxime sulfonates compound.

Oxime sulfonates compound, there is oxime sulfonates residue compound preferably illustration there is the compound of the represented oxime sulfonates residue of formula (b1).

[changing 30]

(in formula (b1), R ⁵represent alkyl or aryl)

Any base also can be substituted, R ⁵alkyl can be straight chain shape and also can be branch-like and also can be ring-type.Below the substituting group of allowing is illustrated.

R ⁵alkyl to be preferably carbon number be 1～10 straight chain shape or branch-like alkyl.R ⁵the alkyl aryl that can be 6～11 through carbon number, alkoxy or the naphthenic base (comprise the bridge connected alicyclic groups such as 7,7-dimethyl-2-oxa-norborny, be preferably bicyclic alkyl etc.) that carbon number is 1～10 replace.

R ⁵aryl to be preferably carbon number be 6～11 aryl, phenyl or naphthyl more preferably.R ⁵aryl can replace through low alkyl group, alkoxy or halogen atom.

The compound that contains the represented oxime sulfonates residue of above-mentioned formula (b1) is particularly preferably formula (OS-3), formula (OS-4) or the represented oxime sulfonates compound of formula (OS-5).

[changing 31]

(in formula (OS-3)～formula (OS-5), R ¹represent alkyl, aryl or heteroaryl, R ²independently represent respectively hydrogen atom, alkyl, aryl or halogen atom, R ⁶independent halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or the alkoxy sulfonyl of representing respectively, X represents O or S, n represent 1 or 2, m represent 0～6 integer)

In above-mentioned formula (OS-3)～formula (OS-5), R ¹alkyl, aryl or heteroaryl also can there is substituting group.

In above-mentioned formula (OS-3)～formula (OS-5), R ¹alkyl be preferably and can there is the alkyl that substituent total carbon number is 1～30.

R ¹the alkyl substituting group that can have can enumerate: halogen atom, alkoxy, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl.

R ¹alkyl can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the second butyl, tributyl, n-pentyl, n-hexyl, n-octyl, positive decyl, dodecyl, trifluoromethyl, perfluoro propyl, perfluoro hexyl, benzyl.

In addition, in above-mentioned formula (OS-3)～formula (OS-5), R ¹aryl be preferably and can there is the aryl that substituent total carbon number is 6～30.

R ¹the aryl substituting group that can have can enumerate: halogen atom, alkyl, alkoxy, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl, sulfonic group, amino-sulfonyl, alkoxy sulfonyl.

R ¹aryl can enumerate: phenyl, p-methylphenyl, rubigan, five chlorophenyl, pentafluorophenyl group, o-methoxyphenyl, to Phenoxyphenyl.

In addition, in above-mentioned formula (OS-3)～formula (OS-5), R ¹heteroaryl be preferably and can there is the heteroaryl that substituent total carbon number is 4～30.

R ¹the heteroaryl substituting group that can have can enumerate: halogen atom, alkyl, alkoxy, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl, sulfonic group, amino-sulfonyl, alkoxy sulfonyl.

In above-mentioned formula (OS-3)～formula (OS-5), R ¹heteroaryl as long as at least one ring is assorted aromatic rings, for example mix aromatic rings and the phenyl ring ring that also can contract.

R ¹heteroaryl can enumerate: can there is the base that removes a hydrogen atom gained in the ring in the cohort that substituent free free thiphene ring, pyrrole ring, thiazole ring, imidazole ring, furan nucleus, benzothiophene ring, benzothiazole ring and benzimidazole ring form.

In above-mentioned formula (OS-3)～formula (OS-5), R ²be preferably hydrogen atom, alkyl or aryl, more preferably hydrogen atom or alkyl.

In above-mentioned formula (OS-3)～formula (OS-5), be present in the plural R in compound ²in, be preferably one or two for alkyl, aryl or halogen atom, more preferably one be alkyl, aryl or halogen atom, be particularly preferably one for alkyl and all the other be hydrogen atom.

In above-mentioned formula (OS-3)～formula (OS-5), R ²alkyl or aryl also can there is substituting group.R ²the alkyl or aryl substituting group that can have can illustration and above-mentioned R ¹the alkyl or aryl identical base of substituting group that can have.

R ²alkyl be preferably and can there is the alkyl that substituent total carbon number is 1～12, more preferably can there is the alkyl that substituent total carbon number is 1～6.

R ²alkyl be preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the second butyl, n-hexyl, allyl, chloromethyl, bromomethyl, methoxy, benzyl, be preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the second butyl, n-hexyl, and then be preferably methyl, ethyl, n-pro-pyl, normal-butyl, n-hexyl, be preferably methyl.

R ²aryl be preferably and can there is the aryl that substituent total carbon number is 6～30.

R ²aryl be particularly preferably phenyl, p-methylphenyl, Chloro-O-Phenyl, rubigan, o-methoxyphenyl, to Phenoxyphenyl.

R ²halogen atom can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.

In these, be preferably chlorine atom, bromine atoms.

In above-mentioned formula (OS-3)～formula (OS-5), X represents O or S, is preferably O.

In formula (OS-3)～formula (OS-5), containing X is 5 Yuans rings or 6 Yuans rings as ring person's ring.

In above-mentioned formula (OS-3)～formula (OS-5), n represents 1 or 2, and during the situation that is O at X, n is preferably 1, and during the situation that is S at X in addition, n is preferably 2.

In above-mentioned formula (OS-3)～formula (OS-5), R ⁶alkyl and alkoxy also can there is substituting group.

In above-mentioned formula (OS-3)～formula (OS-5), R ⁶alkyl be preferably and can there is the alkyl that substituent total carbon number is 1～30.

R ⁶the alkyl substituting group that can have can enumerate: halogen atom, alkoxy, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl.

R ⁶alkyl be preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the second butyl, tributyl, n-pentyl, n-hexyl, n-octyl, positive decyl, dodecyl, trifluoromethyl, perfluoro propyl, perfluoro hexyl, benzyl.

In above-mentioned formula (OS-3)～formula (OS-5), R ⁶alkoxy be preferably and can there is the alkoxy that substituent total carbon number is 1～30.

R ⁶the alkoxy substituting group that can have can enumerate: halogen atom, alkoxy, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl.

R ⁶alkoxy be preferably methoxyl, ethoxy, butoxy, own oxygen base, phenoxy group ethoxy, trichlorine methoxy or ethoxy ethoxy.

In above-mentioned formula (OS-3)～formula (OS-5), R ⁶amino-sulfonyl can enumerate: methylamino sulfonyl, dimethylamino-sulfonyl, phenyl amino sulfonyl, aminomethyl phenyl amino-sulfonyl, amino-sulfonyl.

In above-mentioned formula (OS-3)～formula (OS-5), R ⁶alkoxy sulfonyl can enumerate: methoxyl sulfonyl, ethoxy sulfonyl, propoxyl group sulfonyl, butoxy sulfonyl.

In addition, in above-mentioned formula (OS-3)～formula (OS-5), m represents 0～6 integer, is preferably 0～2 integer, more preferably 0 or 1, be particularly preferably 0.

In addition, the compound that contains the represented oxime sulfonates residue of above-mentioned formula (b1) is particularly preferably any represented oxime sulfonates compound of following formula (OS-6)～formula (OS-11).

[changing 32]

(in formula (OS-6)～formula (OS-11), R ¹represent alkyl, aryl or heteroaryl, R ⁷represent hydrogen atom or bromine atoms, R ⁸represent alkyl, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl that hydrogen atom, carbon number are 1～8, R ⁹represent hydrogen atom, halogen atom, methyl or methoxy, R ¹⁰represent hydrogen atom or methyl)

R in formula (OS-6)～formula (OS-11) ¹with the R in above-mentioned formula (OS-3)～formula (OS-5) ¹for identical meanings, preferred aspects is also identical.

R in formula (OS-6) ⁷represent hydrogen atom or bromine atoms, be preferably hydrogen atom.

R in formula (OS-6)～formula (OS-11) ⁸represent alkyl, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl that hydrogen atom, carbon number are 1～8, be preferably carbon number and be 1～8 alkyl, halogen atom or phenyl, the alkyl that more preferably carbon number is 1～8, and then to be preferably carbon number be 1～6 alkyl, be particularly preferably methyl.

R in formula (OS-8) and formula (OS-9) ⁹represent hydrogen atom, halogen atom, methyl or methoxy, be preferably hydrogen atom.

R in formula (OS-8)～(OS-11) ¹⁰represent hydrogen atom or methyl, be preferably hydrogen atom.

In addition, in above-mentioned oxime sulfonates compound, the spatial structure (E, Z) about oxime, can be any, also can be potpourri.

The concrete example of the oxime sulfonates compound that above-mentioned formula (OS-3)～formula (OS-5) is represented can be enumerated following exemplary compounds, but the present invention is not limited to these compounds.

[changing 33]

[changing 34]

[changing 35]

[changing 36]

[changing 37]

[changing 38]

[changing 39]

The above-claimed cpd that contains the represented oxime sulfonates residue of formula (b1) is preferably the represented compound of formula (OS-1).

[changing 40]

In above-mentioned general formula (OS-1), R ¹represent hydrogen atom, alkyl, thiazolinyl, alkoxy, alkoxy carbonyl, acyl group, amine formyl, sulfamic, sulfo group, cyano group, aryl or heteroaryl.R ²represent alkyl or aryl.

Represent-O-of X ,-S-,-NH-,-NR ⁵-,-CH ₂-,-CR ⁶h-or-CR ⁶r ⁷-, R ⁵～R ⁷represent alkyl or aryl.

R ²¹～R ²⁴independently represent respectively hydrogen atom, halogen atom, alkyl, thiazolinyl, alkoxy, amino, alkoxy carbonyl, alkyl-carbonyl, aryl carbonyl, amide group, sulfo group, cyano group or aryl.R ²¹～R ²⁴in two also can distinguish mutual bond and form ring.

R ²¹～R ²⁴be preferably hydrogen atom, halogen atom and alkyl, in addition, also separately can preferably enumerate R ²¹～R ²⁴in at least two mutual bonds and form the aspect of aryl.Wherein, with regard to the viewpoint of sensitivity, be preferably R ²¹～R ²⁴be the aspect of hydrogen atom.

Above-mentioned functional group all also can further have substituting group.

The represented compound of above-mentioned formula (OS-1) is the represented compound of following formula (OS-2) more preferably.

[changing 41]

In above-mentioned formula (OS-2), R ¹, R ², R ²¹～R ²⁴be identical meanings with the middle person of formula (OS-1) respectively, preference is also identical in addition.

In these, the R in formula (OS-1) and formula (OS-2) more preferably ¹for the aspect of cyano group or aryl, most preferably be the represented and R of formula (OS-2) ¹aspect for cyano group, phenyl or naphthyl.

In addition, in above-mentioned oxime sulfonates compound, the spatial structure (E, Z etc.) about oxime or benzothiazole ring, can be respectively any, also can be potpourri.

Below illustrate can be suitably for the concrete example (exemplary compounds b-1～exemplary compounds b-34) of the represented compound of the present invention's formula (OS-1), but the present invention is not limited to this.Moreover Me represents methyl, Et represents ethyl, and Bn represents benzyl, and Ph represents phenyl.

[changing 42]

[changing 43]

[changing 44]

[changing 45]

In above-claimed cpd, with regard to having the viewpoint of sensitivity and stability concurrently, be preferably b-9, b-16, b-31, b-33.

The above-claimed cpd that contains the represented oxime sulfonates residue of formula (b1) also can be the represented oxime sulfonates compound of following formula (b2).

[changing 46]

(in formula (b2), R ⁵represent alkyl or aryl, X represents alkyl, alkoxy or halogen atom, and m represents 0～3 integer, and m is 2 or 3 o'clock, a plurality of X can be identical also can be different)

As the alkyl of X, being preferably carbon number is 1～4 straight chain shape or branch-like alkyl.

As the alkoxy of X, being preferably carbon number is 1～4 straight chain shape or branch-like alkoxy.

Halogen atom as X is preferably chlorine atom or fluorine atom.

M is preferably 0 or 1.

Being particularly preferably m in formula (b2) is that 1, X is methyl, and the position of substitution of X is ortho position, R ⁵for carbon number be 1～10 straight chain-like alkyl, 7,7-dimethyl-2-oxa-norborny methyl or the compound to toluyl groups.

The compound that contains the represented oxime sulfonates residue of formula (b1) also can be the represented oxime sulfonates compound of formula (b3).

[changing 47]

(in formula (b3), R ⁵with the R in formula (b1) ⁵for identical meanings, the alkyl that X ' expression halogen atom, hydroxyl, carbon number are 1～4, alkoxy, cyano group or the nitro that carbon number is 1～4, L represents 0～5 integer)

R in formula (b3) ⁵be preferably methyl, ethyl, n-pro-pyl, normal-butyl, n-octyl, trifluoromethyl, pentafluoroethyl group, perfluor n-pro-pyl, perfluor normal-butyl, p-methylphenyl, 4-chlorphenyl or pentafluorophenyl group, be particularly preferably n-octyl.

It is 1～5 alkoxy that X ' is preferably carbon number, more preferably methoxyl.

L is preferably 0～2, is particularly preferably 0～1.

The concrete example of the compound that formula (b3) is represented can be enumerated: α-(sulfonyloxy methyl oxygen base imino group) benzyl cyanide, α-(ethyl sulfonyloxy imino group) benzyl cyanide, α-(n-pro-pyl sulfonyloxy imino group) benzyl cyanide, α-(normal-butyl sulfonyloxy imino group) benzyl cyanide, α-(4-tosyloxy imino group) benzyl cyanide, α-[(sulfonyloxy methyl oxygen base imino group)-4-methoxyphenyl] acetonitrile, α-[(ethyl sulfonyloxy imino group)-4-methoxyphenyl] acetonitrile, α-[(n-pro-pyl sulfonyloxy imino group)-4-methoxyphenyl] acetonitrile, α-[(normal-butyl sulfonyloxy imino group)-4-methoxyphenyl] acetonitrile, α-[(4-tosyloxy imino group)-4-methoxyphenyl] acetonitrile.

The concrete example of preferred oxime sulfonates compound can be enumerated following compound (i)～compound (viii) etc., can be used alone a kind of or and with two or more.Compound (i)～compound (viii) can be used as commercially available product and obtains.In addition, also can be used in combination with (C) radiation acid producing agent of other kinds.

[changing 48]

In photosensitive polymer combination of the present invention, the total solid composition of photosensitive polymer combination of take is benchmark, and the content of light acid producing agent is preferably 1 quality %～30 quality %, more preferably 3 quality %～20 quality %.

Acid producing agent can be used alone a kind of or is used in combination two or more.Be used in combination when two or more, being preferably the total atom number except hydrogen atom is that more than 2 different two kinds produce organic acid compound combinations.

(b2) sensitizer

In composition of the present invention, in order to absorb active ray or radioactive ray, promote the decomposition of above-mentioned sulfonium salt, also can add sensitizer.Sensitizer absorbs active ray or radioactive ray and becomes electron excitation state.The sensitizer that becomes electron excitation state contacts with sulfonium, produces the effects such as electron transfer, energy transfer, heating.Thus, polymerization initiator generation chemical change and decomposing, generates free radical, acid or alkali.

Preferably the example of sensitizer can be enumerated the compound that belongs to following compounds and have absorbing wavelength in the scope of 350nm to 450nm.

The polynuclear aromatic same clan (pyrene for example, perylene, triphenylene (triphenylene), anthracene), the dibenzo piperazine class (luciferin (fluorescein) for example of muttering, eosin, erythrosine (erythrosine), rhodamine B, rose-red (rose bengal)), cyanine (cyanine) class (sulphur carbon cyanines for example, oxa-carbocyanine), merocyanine class (merocyanine for example, carbonyl merocyanine), thiazide (thionine (thionin) for example, methylene blue, toluidine blue), acridine (acridine orange for example, chloroflavin, acridine yellow (acriflavine)), Anthraquinones (for example anthraquinone), the sour cyanines class in side (for example sour cyanines in side), Coumarins (for example 7-diethylamino-4-methylcoumarin).

The example of preferred sensitizer can be enumerated the represented compound of following formula (IX)～formula (XIV).

[changing 49]

In formula (IX), A ¹represent sulphur atom or NR ⁵⁰, R ⁵⁰represent alkyl or aryl, L ²represent the A with adjacency ¹and adjoining carbons form the nonmetallic atom group of the alkaline core of pigment, R jointly ⁵¹, R ⁵²independently represent respectively the nonmetallic atom group of hydrogen atom or monovalence, R ⁵¹, R ⁵²also bond and form the acid core of pigment mutually.W represents oxygen atom or sulphur atom.

[changing 50]

In formula (X), Ar ¹and Ar ²independently represent respectively aryl, via-L ³-bond and link.Herein, L ³expression-O-or-S-.In addition, shown in W and formula (IX), person is identical meanings.

[changing 51]

In formula (XI), A ²represent sulphur atom or NR ⁵⁹, L ⁴represent the A with adjacency ²and carbon atom forms the nonmetallic atom group of the alkaline core of pigment, R jointly ⁵³, R ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷and R ⁵⁸independently represent respectively the base of the nonmetallic atom group of monovalence, R ⁵⁹represent alkyl or aryl.

[changing 52]

In formula (XII), A ³, A ⁴respectively independent expression-S-,-NR ⁶²-or-NR ⁶³-, R ⁶², R ⁶³the alkyl that independent expression is substituted or is unsubstituted respectively, the aryl that is substituted or is unsubstituted, L ⁵, L ⁶independently represent respectively the A with adjacency ³, A ⁴and adjoining carbons form the nonmetallic atom group of the alkaline core of pigment, R jointly ⁶⁰, R ⁶¹respectively independent is the nonmetallic atom group of hydrogen atom or monovalence, or bond and form the ring of aliphatics or aromatic series mutually.

[changing 53]

In formula (XIII), R ⁶⁶expression can have substituent aromatic ring or heterocycle, A ⁵represent oxygen atom, sulphur atom or=NR ⁶⁷.R ⁶⁴, R ⁶⁵and R ⁶⁷independently represent respectively the nonmetallic atom group of hydrogen atom or monovalence, R ⁶⁷with R ⁶⁴, and R ⁶⁵with R ⁶⁷can distinguish mutual bond to form the ring of aliphatics or aromatic series.

[changing 54]

In formula (XIV), R ₆₈and R ₆₉independently represent respectively the nonmetallic atom group of hydrogen atom or monovalence.R ₇₀and R ₇₁the nonmetallic atom group n of independent expression monovalence represents 0～4 integer respectively.At n, be 2 when above, R ₇₀, R ₇₁can distinguish mutual bond to form the ring of aliphatics or aromatic series.

Sensitizer is particularly preferably anthracene derivant.

The preferred concrete example of the compound that formula (IX)～formula (XIV) is represented can be enumerated following (C-1) illustrating～(C-26), but is not limited to these compounds.

[changing 55]

[changing 56]

[changing 57]

[changing 58]

Sensitizer as above can be used commercially available product, or also can synthesize by known synthetic method.

In photosensitive polymer combination of the present invention, the total solid composition of photosensitive polymer combination of take is benchmark, and the content of sensitizer is preferably 1 quality %～30 quality %, more preferably 3 quality %～20 quality %.

(c) alkali compounds

Composition of the present invention is preferably and contains alkali compounds, with reduce from exposure to till heating through time performance change.

Alkali compounds preferably can be enumerated the compound with the structure shown in following formula (A)～formula (E).

[changing 59]

In general formula (A) and general formula (E),

R ²⁰⁰, R ²⁰¹and R ²⁰²can be identical also can be different, represent hydrogen atom, alkyl (being preferably carbon number is 1～20), naphthenic base (being preferably carbon number is 3～20) or aryl (carbon number is 6～20), herein, R ²⁰¹with R ²⁰²also bond and form ring mutually.

R ²⁰³, R ²⁰⁴, R ²⁰⁵and R ²⁰⁶can be identical also can be different, represent that carbon number is the alkyl of 1～20.

About abovementioned alkyl, there is substituent alkyl and be preferably the cyano group alkyl that carbon number is 1～20 aminoalkyl, carbon number is 1～20 hydroxy alkyl or carbon number are 1～20.

Alkyl in these general formulas (A) and general formula (E) is more preferably unsubstituted.

Preferred compound can be enumerated: guanidine, amino-pyrroles pyridine, pyrazoles, pyrazoline, piperazine, amino morpholine, aminoalkyl morpholine, piperidines etc., preferred compound can be enumerated: the compound with glyoxaline structure, diazabicyclo structure, oxyhydroxide structure, carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, the alkylamine derivative with hydroxyl and/or ehter bond, has the anil of hydroxyl and/or ehter bond etc.

The compound with glyoxaline structure can be enumerated: imidazoles, 2,4,5-triphenyl imidazoles, benzimidazole, 2-Phenylbenzimidazole etc.The compound with diazabicyclo structure can be enumerated: Isosorbide-5-Nitrae-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3, the 0] ninth of the ten Heavenly Stems-5-alkene, 1,8-diazabicyclo [5,4,0] 11-7-alkene etc.The compound with oxyhydroxide structure can be enumerated tetrabutylammonium, triaryl matte oxyhydroxide, phenacyl sulfonium oxyhydroxide, have the sulfonium oxyhydroxide of 2-oxa alkyl, specifically can enumerate triphenylsulfonium oxyhydroxide, three (tributyl phenyl) sulfonium oxyhydroxide, two (tributyl phenyl) Iodonium oxyhydroxide, phenacyl thiophene oxyhydroxide, 2-oxa-propyl group thiophene oxyhydroxide etc.The compound with carboxylate structure is that the negative ion portion with the compound of oxyhydroxide structure becomes the carboxylate person of forming, such as enumerating acetate, diamantane-1-carboxylate, perfluoroalkyl carboxylate etc.The compound with trialkylamine structure can be enumerated three (normal-butyl) amine, three (n-octyl) amine etc.Aniline compound can be enumerated: 2,6-DIPA, DMA, N, N-dibutyl aniline, N, N-dihexyl aniline etc.The alkylamine derivative with hydroxyl and/or ehter bond can be enumerated: monoethanolamine, diethanolamine, triethanolamine, N-phenyldiethanol-amine, three (methoxyethoxyethyl) amine etc.The anil with hydroxyl and/or ehter bond can be enumerated N, two (hydroxyethyl) aniline of N-etc.

Preferred alkali compounds and then can enumerate: have phenoxy group amines, have phenoxy group ammonium salt compound, there is the amines of sulfonate group and there is the ammonium salt compound of sulfonate group.

Amines can be used one-level, secondary, the amines of three grades, and the alkyl that is preferably at least one is binding on the amines of nitrogen-atoms.Amines is tertiary amine compound more preferably.Amines is as long as at least one alkyl (being preferably carbon number is 1～20) is binding on nitrogen-atoms, and, except alkyl, naphthenic base (being preferably carbon number is 3～20) or aryl (being preferably carbon number is 6～12) also can be binding on nitrogen-atoms.Amines is preferably and in alkyl chain, contains oxygen atom and form oxyalkylene.The number of oxyalkylene is more than 1 in molecule, is preferably 3～9, and then is preferably 4～6.In oxyalkylene, be preferably oxygen ethylidene (CH ₂cH ₂o-) or oxygen propylidene (CH (CH ₃) CH ₂o-or-CH ₂cH ₂cH ₂and then be preferably oxygen ethylidene O-).

Ammonium salt compound can be used one-level, secondary, three grades, the ammonium salt compound of level Four, is preferably the ammonium salt compound that at least one alkyl is binding on nitrogen-atoms.Ammonium salt compound is as long as at least one alkyl (being preferably carbon number is 1～20) is binding on nitrogen-atoms, and, except alkyl, naphthenic base (being preferably carbon number is 3～20) or aryl (being preferably carbon number is 6～12) also can be binding on nitrogen-atoms.Ammonium salt compound is preferably and in alkyl chain, contains oxygen atom and form oxyalkylene.The number of oxyalkylene is more than 1 in molecule, is preferably 3～9, and then is preferably 4～6.In oxyalkylene, be preferably oxygen ethylidene (CH ₂cH ₂o-) or oxygen propylidene (CH (CH ₃) CH ₂o-or-CH ₂cH ₂cH ₂and then be preferably oxygen ethylidene O-).

The negative ion of ammonium salt compound can be enumerated halogen atom, sulfonate, borate, phosphate etc., is wherein preferably halogen atom, sulfonate.Halogen atom is particularly preferably chloride, bromide, iodide, and it is 1～20 organic sulfonate that sulfonate is particularly preferably carbon number.It is 1～20 alkyl sulfonate, arylsulphonate that organic sulfonate can be enumerated carbon number.The alkyl of alkyl sulfonate also can have substituting group, and substituting group is such as enumerating fluorine, chlorine, bromine, alkoxy, acyl group, aryl etc.Alkyl sulfonate specifically can be enumerated: mesylate, esilate, fourth sulfonate, own sulfonate, pungent sulfonate, benzyl sulfonate, fluoroform sulphonate, five fluorine esilates, nine fluorine fourth sulfonate etc.The aryl of arylsulphonate can be enumerated phenyl ring, naphthalene nucleus, anthracene nucleus.Phenyl ring, naphthalene nucleus, anthracene nucleus also can have substituting group, and it is the naphthenic base that 1～6 straight chain or branch's alkyl, carbon number are 3～6 that substituting group is preferably carbon number.Straight chain or branch's alkyl, naphthenic base specifically can be enumerated: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, tributyl, n-hexyl, cyclohexyl etc.Other substituting groups can be enumerated: the alkoxy that carbon number is 1～6, halogen atom, cyano group, nitro, acyl group, acyloxy etc.

What is called have phenoxy group amines, there is the ammonium salt compound of phenoxy group, refer to there is the compound of phenoxy group at the alkyl of amines or ammonium salt compound with the nitrogen-atoms end that is opposition side.Phenoxy group also can have substituting group.The substituting group of phenoxy group is such as enumerating: alkyl, alkoxy, halogen atom, cyano group, nitro, carboxyl, carboxylic acid ester groups, sulfonate group, aryl, aralkyl, acyloxy, aryloxy group etc.Substituent replacement position can be any of 2～6.Substituent number can be any in 1～5 scope.

Be preferably and between phenoxy group and nitrogen-atoms, there is at least one oxyalkylene.The number of oxyalkylene is more than 1 in molecule, is preferably 3～9, and then is preferably 4～6.In oxyalkylene, be preferably oxygen ethylidene (CH ₂cH ₂o-) or oxygen propylidene (CH (CH ₃) CH ₂o-or-CH ₂cH ₂cH ₂and then be preferably oxygen ethylidene O-).

Have sulfonate group amines, there is any that sulfonate group in the ammonium salt compound of sulfonate group also can be alkyl sulfonic ester, naphthenic base sulphonic acid ester, aromatic yl sulphonate, during the situation of alkyl sulfonic ester, it is 1～20 that alkyl is preferably carbon number, during the situation of naphthenic base sulphonic acid ester, it is 3～20 that naphthenic base is preferably carbon number, during the situation of aromatic yl sulphonate, it is 6～12 that aryl is preferably carbon number.Alkyl sulfonic ester, naphthenic base sulphonic acid ester, aromatic yl sulphonate also can have substituting group, and substituting group is preferably halogen atom, cyano group, nitro, carboxyl, carboxylic acid ester groups, sulfonate group.

Be preferably and between sulfonate group and nitrogen-atoms, there is at least one oxyalkylene.The number of oxyalkylene is more than 1 in molecule, is preferably 3～9, and then is preferably 4～6.In oxyalkylene, be preferably oxygen ethylidene (CH ₂cH ₂o-) or oxygen propylidene (CH (CH ₃) CH ₂o-or-CH ₂cH ₂cH ₂and then be preferably oxygen ethylidene O-).

In addition, following compound also as alkali compounds and preferably.

[changing 60]

These alkali compounds can be used alone a kind of, and also use capable of being combined is two or more.

Composition of the present invention can contain also alkali-free compound, and when the situation containing, the total solid composition of composition of take is benchmark, and the content of alkali compounds is generally 0.001 quality %～10 quality %, is preferably 0.01 quality %～5 quality %.

The usage ratio of acid producing agent and alkali compounds is preferably acid producing agent/alkali compounds (mol ratio)=2.5～300.That is, with regard to the aspect of sensitivity, resolving power, mol ratio is preferably more than 2.5, with regard to suppressing until after exposure heat treated through time relief pattern thick due to the aspect that reduces of resolving power with regard to, be preferably below 300.Acid producing agent/alkali compounds (mol ratio) more preferably 5.0～200, and then be preferably 7.0～150.

(d) thermal acid generator

In the present invention, also can contain thermal acid generator.So-called thermal acid generator, refer to the acidic compound by heat, the compound that to be generally thermal decomposition point be 130 ℃～250 ℃, be preferably the scope of 150 ℃～220 ℃, such as for by heating the sour compound of low nucleophilicities such as producing sulfonic acid, carboxylic acid, disulfonyl imines.

Produce that acid is preferably the sulfonic acid of pKa below by force to 2 or the alkyl or aryl carboxylic acid replacing through electron-withdrawing group, the disulfonyl imines that similarly replaces through electron-withdrawing group etc.Electron-withdrawing group can be enumerated: haloalkyl, nitro, the cyano group such as the halogen atoms such as F atom, trifluoromethyl.

For thermal acid generator, require through time preserve in or in pre-bake step after coating composition, do not decompose, and decompose rapidly in the heat hardening step after patterning.Therefore, thermal decomposition point is preferably 100 ℃～300 ℃.More preferably 120 ℃～250 ℃, and then be preferably 150 ℃～200 ℃.

Thermal acid generator can apply above-mentioned passing through and expose and acidic smooth acid producing agent.Such as enumerating: the salt such as sulfonium salt Huo Iodonium salt, N-hydroxyl acid imide sulfonate compound, oxime sulfonates, adjacent nitrobenzyl sulfonate esters etc.

Preferred sulfonium salt for example can be enumerated the represented compound of following general formula (TA-1)～general formula (TA-3).

[changing 61]

In general formula (TA-1),

R _t1～R _t5independently represent respectively hydrogen atom, alkyl, naphthenic base, alkoxy or halogen atom.

R _t6and R _t7independently represent respectively hydrogen atom, alkyl or cycloalkyl.

R _t8and R _t9independently represent respectively alkyl, naphthenic base, allyl or vinyl.

R _t1～R _t5in any two above, R _t6with R _t7and R _t8with R _t9also can distinguish bond and form ring structure, this ring structure also can contain oxygen atom, sulphur atom, ketonic bond, ester bond, amido link.

R _t1～R _t5in any two above, R _t6with R _t7and R _t8with R _t9bond and the base that forms can be enumerated butylidene, pentylidene etc.

X ^-represent non-nucleophilicity negative ion, as mentioned above, the disulfonyl imines that be preferably the sulfonic acid of pKa below by force to 2 or the alkyl or aryl carboxylic acid replacing through electron-withdrawing group, similarly replaces through electron-withdrawing group etc.Electron-withdrawing group can be enumerated: haloalkyl, nitro, the cyano group such as the halogen atoms such as F atom, trifluoromethyl.

In general formula (TA-2),

R _t10and R _t11independently represent respectively alkyl, naphthenic base, allyl or vinyl.

R _t10and R _t11also can distinguish bond and form ring structure, this ring structure also can contain oxygen atom, sulphur atom, ketonic bond, ester bond, amido link.

R _t10with R _t11bond and the base that forms can be enumerated butylidene, pentylidene etc.

R _t12～R _t16independent hydrogen atom, alkyl, naphthenic base, aryl, alkoxy, thioalkoxy group, the hydroxyl of representing respectively, two also bonds and form the Ppolynuclear aromatic rings such as naphthalene nucleus, anthracene nucleus mutually above.

X ^-represent non-nucleophilicity negative ion.

In general formula (TA-3),

R _t17represent alkyl (straight chain or branch) or naphthenic base, can enumerate being preferably that carbon number is 1～20, more preferably carbon number is straight chain and branch's alkyl (for example methyl, ethyl, straight chain or branch's propyl group, straight chain or branch's butyl, straight chain or branch's amyl group) of 1～12.Naphthenic base not only can be enumerated the cyclic alkyl of the monocycle of cyclopentyl, cyclohexyl and so on, also can enumerate the cyclic alkyl with bridge joint position of norborny, three ring decyls, adamantyl and so on.

R _t18and R _t19independently represent respectively hydrogen atom, alkyl or cycloalkyl.

R _t20and R _t21independently represent respectively alkyl, naphthenic base, allyl or vinyl.

R _t18with R _t19and R _t20with R _t21also can distinguish bond and form ring structure, this ring structure also can contain oxygen atom, sulphur atom, ketonic bond, ester bond, amido link.R _t18with R _t19and R _t20with R _t21bond and the base that forms can be enumerated butylidene, pentylidene etc.

X ^-represent non-nucleophilicity negative ion.

As R _t1～R _t17alkyl can be any of straight chain, branch-like, for example can to enumerate carbon number be 1～20, be preferably carbon number is straight chain and branch's alkyl (for example methyl, ethyl, straight chain or branch's propyl group, straight chain or branch's butyl, straight chain or branch's amyl group) of 1～12.

As R _t1～R _t17naphthenic base mean not only to comprise the alkyl of monocycle, and also comprise the cyclic alkyl that encircles more, has bridge joint position, as R _t12～R _t16naphthenic base to be preferably carbon number be the naphthenic base (for example cyclopentyl, cyclohexyl) of 3～8.

As R _t17naphthenic base be also preferably the cyclic alkyl with bridge joint position that carbon number is the naphthenic base (for example cyclopentyl, cyclohexyl) of 3～8 and norborny, three ring decyls, adamantyl and so on.

As R _t1～R _t5, R _t12～R _t16alkoxy can be any of straight chain, branch, ring-type, for example can enumerate carbon number and be 1～10 alkoxy, the cyclic alkoxy (for example cyclopentyloxy, cyclohexyloxy) that preferably can to enumerate carbon number and be 1～5 straight chain and branch's alkoxy (for example methoxyl, ethoxy, straight chain or branch's propoxyl group, straight chain or branch's butoxy, straight chain or branch's amoxy), carbon number be 3～8.

As R _t12～R _t16thioalkoxy group can be any of straight chain, branch, ring-type, for example can enumerate carbon number and be 1～10 thioalkoxy group, the ring-type thioalkoxy group (for example sulphur cyclopentyloxy, sulphur cyclohexyloxy) that preferably can to enumerate carbon number and be 1～5 straight chain and branch's thioalkoxy group (for example sulphur methoxyl, sulphur ethoxy, straight chain or branch's sulphur propoxyl group, straight chain or branch's sulphur butoxy, straight chain or branch's sulphur amoxy), carbon number be 3～8.

As X ^-non-nucleophilicity negative ion be preferably organic anion, be particularly preferably the organic anion shown in following general formula.

[changing 62]

In above-mentioned general formula,

Rc ₁represent organic group.

Rc ₁organic group can to enumerate carbon number be 1～30 base, preferably can enumerate: can there are substituent alkyl, naphthenic base, aryl or a plurality of through singly-bound ,-O-,-CO in these ₂-,-S-,-SO ₃-,-SO ₂n (Rd ₁the base that concatenating group such as)-wait links.

Rd ₁represent hydrogen atom or alkyl.

Rc ₂represent that 1 through the alkyl of fluorine atom or fluoroalkyl replacement.

Rc ₃and Rc ₄independently represent that respectively 1 through the alkyl of fluorine atom or fluoroalkyl replacement.Be preferably carbon number and be 1～4 perfluoroalkyl.

Rc ₃with Rc ₄also bond and form ring mutually.

Rc ₃with Rc ₄bond and the base that forms can be enumerated alkylidene, cycloalkylidene, arlydene.Be preferably carbon number and be 2～4 sub-perfluoroalkyl.

You Xuan Iodonium salt can be enumerated the represented compound of following general formula (TA-4).

[changing 63]

In formula (TA-4), R ₄₁and R ₄₂represent respectively hydrogen atom, can there is substituent alkyl, can there is substituent naphthenic base, can there is substituent alkoxy, can there is substituent alkoxy carbonyl, can there is substituent acyl group, can there is substituent acyloxy, nitro, halogen atom, hydroxyl, carboxyl.

A represents that 1～5, b represents 1～5.

Wherein, R ₄₁and R ₄₂at least one represent that carbon number is 5 and above has substituent alkyl, can have substituent naphthenic base, can have substituent alkoxy, can have substituent alkoxy carbonyl, can have substituent acyl group, can have substituent acyloxy.

X represents R-SO ₃, R represents can have substituent aliphatic alkyl, can have substituent aromatic hydrocarbyl.

R ₄₁and R ₄₂alkyl can enumerate: the carbon number can with substituent methyl, ethyl, propyl group, normal-butyl, isobutyl, the second butyl, tributyl, amyl group, hexyl, heptyl, octyl group, the 3rd amyl group, decyl, dodecyl, cetyl and so on is the base of 1～25.Naphthenic base can be enumerated: the carbon number can with substituent cyclopropyl, cyclopentyl, cyclohexyl, ring octyl group, cyclo-dodecyl, ring cetyl etc. and so on is the base of 3～25.Alkoxy can be enumerated: the carbon number can with substituent methoxyl, ethoxy, propoxyl group, isopropoxy, n-butoxy, isobutoxy, the second butoxy or the 3rd butoxy, amoxy, the 3rd amoxy, just own oxygen base, n-octyloxy, n-dodecane oxygen base etc. and so on is the base of 1～25.

Alkoxy carbonyl can be enumerated: the carbon number can with substituent methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, n-butoxy carbonyl, isobutoxy carbonyl, the second butoxy carbonyl or the 3rd butoxy carbonyl, pentyloxy carbonyl, the 3rd pentyloxy carbonyl, positive hexyloxy carbonyl, n-octyloxy carbonyl, n-dodecane oxygen base carbonyl etc. and so on is the base of 2～25.Acyl group can be enumerated: the carbon number can with substituent formoxyl, acetyl group, bytyry, valeryl, caproyl, caprylyl, tributyl carbonyl, the 3rd amyl group carbonyl etc. and so on is the base of 1～25.Acyloxy can be enumerated: the carbon number can with substituent acetoxyl group, propionyloxy, butyryl acyloxy, the 3rd butyryl acyloxy, the three penta acyloxy, normal hexane carbonyl oxygen base, normal octane carbonyl oxygen base, n-dodecane carbonyl oxygen base, n-hexadecane carbonyl oxygen base etc. and so on is the base of 2～25.Halogen atom can be enumerated fluorine atom, chlorine atom, bromine atoms or iodine atom.

To the substituting group of these bases, preferably can enumerate: carbon number is alkoxy, halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom), acyl group, acyloxy, cyano group, hydroxyl, carboxyl, alkoxy carbonyl, nitro of 1～4 etc.Moreover, as mentioned above, R ¹, R ²at least one represent that carbon number is 5 and above has substituent alkyl, can have substituent naphthenic base, can have substituent alkoxy, can have substituent alkoxy carbonyl, can have substituent acyl group, can have substituent acyloxy.Above-mentioned these carbon numbers are that can to enumerate carbon number in above-mentioned concrete example be the base of 5～25 to 5 above substituting groups.

In above-mentioned, as R ₄₁and R ₄₂the substituent alkyl that has be preferably methyl, ethyl, propyl group, isopropyl, butyl, tributyl, n-pentyl, the 3rd amyl group, n-hexyl, n-octyl, decyl, naphthenic base is preferably can have substituent cyclohexyl, ring octyl group, cyclo-dodecyl, alkoxy is preferably can have substituent methoxyl, ethoxy, isopropoxy, n-butoxy, the second butoxy, the 3rd butoxy, amoxy, the 3rd amoxy, just own oxygen base, n-octyloxy, n-dodecane oxygen base, alkoxy carbonyl is preferably can have substituent methoxycarbonyl, ethoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, the second butoxy carbonyl, the 3rd butoxy carbonyl, pentyloxy carbonyl, the 3rd pentyloxy carbonyl, positive hexyloxy carbonyl, n-octyloxy carbonyl, n-dodecane oxygen base carbonyl, acyl group is preferably can have substituent formoxyl, acetyl group, bytyry, valeryl, caproyl, caprylyl, tributyl carbonyl, the 3rd amyl group carbonyl, acyloxy is preferably can have substituent acetoxyl group, propionyloxy, butyryl acyloxy, the 3rd butyryl acyloxy, the three penta acyloxy, normal hexane carbonyl oxygen base, normal octane carbonyl oxygen base.

In addition, carbon number is that 5 above substituent alkyl that have are preferably n-pentyl, the 3rd amyl group, n-hexyl, n-octyl, decyl.Carbon number is that 5 above substituent naphthenic base that have are preferably cyclohexyl, ring octyl group, cyclo-dodecyl.Carbon number is that 5 above substituent alkoxys that have are preferably amoxy, the 3rd amoxy, own oxygen base, n-octyloxy, dodecyloxy.Carbon number is that 5 above substituent alkoxy carbonyls that have are preferably pentyloxy carbonyl, the 3rd pentyloxy carbonyl, hexyloxy carbonyl, n-octyloxy carbonyl, dodecyloxy carbonyl.Carbon number is that 5 above substituent acyl groups that have are preferably valeryl, caproyl, caprylyl, the 3rd amyl group carbonyl.Carbon number is 5 above had substituent acyloxy and is preferably the three penta acyloxy, normal hexane carbonyl oxygen base, normal octane carbonyl oxygen base.The substituting group of these bases is preferably to methoxyl, ethoxy, the 3rd butoxy, chlorine atom, bromine atoms, cyano group, hydroxyl, methoxycarbonyl, ethoxy carbonyl, the 3rd butoxy carbonyl, the 3rd pentyloxy carbonyl.

The represented Iodonium compound of the general formula using in the present invention (TA-4) use as above-mentioned as there is ad hoc structure sulfonic acid as its counter anion X ^-.R in counter anion has substituent aliphatic alkyl and can enumerate the alkyl that carbon number is the 1～straight chain of 20 or the alkyl of branch or ring-type.In addition, R can enumerate and can have substituent aromatic series base.The alkyl of above-mentioned R can be enumerated: can have the base that the carbon numbers such as substituent methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, decyl, dodecyl are 1～20.Cyclic alkyl can be enumerated: can have substituent cyclopentyl, cyclohexyl, ring octyl group, cyclo-dodecyl, adamantyl, norborny, camphoryl, three ring decyls, menthyl etc.Aromatic series base can be enumerated: can have substituent phenyl, naphthyl.

In above-mentioned, R has substituent alkyl and can enumerate methyl, trifluoromethyl, ethyl, pentafluoroethyl group, 2,2,2-trifluoroethyl, n-pro-pyl, normal-butyl, nine fluorine butyl, n-pentyl, n-hexyl, n-octyl, 17 fluorine octyl groups, 2-ethylhexyl, decyl, dodecyl, cyclic alkyl can be enumerated cyclopentyl, cyclohexyl, camphoryl.Aromatic series base can be enumerated: can have substituent phenyl, naphthyl, pentafluorophenyl group, to toluyl groups, to fluorophenyl, rubigan, p-hydroxybenzene, p-methoxyphenyl, dodecylphenyl, trimethylphenyl (mesityl), triisopropyl phenyl, 4-hydroxyl-1-naphthyl, 6-hydroxyl-2-naphthyl.

In above-mentioned each substituting group, preferred R ₄₁and R ₄₂concrete example be methyl, ethyl, propyl group, isopropyl, normal-butyl, tributyl, n-pentyl, the 3rd amyl group, n-hexyl, n-octyl, cyclohexyl, methoxyl, ethoxy, isopropoxy, n-butoxy, the 3rd butoxy, amoxy, the 3rd amoxy, own oxygen base, n-octyloxy, methoxycarbonyl, ethoxy carbonyl, n-butoxy carbonyl, the 3rd butoxy carbonyl, the 3rd pentyloxy carbonyl, hexyloxy carbonyl, n-octyloxy carbonyl, formoxyl, acetyl group, bytyry, caproyl, caprylyl, tributyl carbonyl, the 3rd amyl group carbonyl, acetoxyl group, propionyloxy, butyryl acyloxy, the 3rd butyryl acyloxy, the three penta acyloxy, normal hexane carbonyl oxygen base, normal octane carbonyl oxygen base, hydroxyl, chlorine atom, bromine atoms, nitro.Preferred carbon number is that the concrete example of 5 above bases is n-pentyl, the 3rd amyl group, n-hexyl, n-octyl, decyl, cyclohexyl, amoxy, the 3rd amoxy, own oxygen base, n-octyloxy, dodecyloxy, pentyloxy carbonyl, the 3rd pentyloxy carbonyl, hexyloxy carbonyl, n-octyloxy carbonyl, dodecyloxy carbonyl, valeryl, caproyl, caprylyl, the 3rd amyl group carbonyl, the three penta acyloxy, normal hexane carbonyl oxygen base, normal octane carbonyl oxygen base.

The concrete example of preferred sulfonic acid substituent R is methyl, trifluoromethyl, ethyl, pentafluoroethyl group, 2; 2,2-trifluoroethyl, normal-butyl, nine fluorine butyl, n-hexyl, n-octyl, 17 fluorine octyl groups, 2-ethylhexyl, camphoryl, phenyl, naphthyl, pentafluorophenyl group, to toluyl groups, to fluorophenyl, rubigan, p-methoxyphenyl, dodecylphenyl, trimethylphenyl, triisopropyl phenyl, 4-hydroxyl-1-naphthyl, 6-hydroxyl-2-naphthyl.

The sour total carbon number producing is preferably 1～30.More preferably 1～28, and then be preferably 1～25.When its total carbon number is less than the situation of 1, sometimes because causing, volatilization resolves the bad obstacle that waits, if surpass 30, sometimes produce development residue etc. and not good enough.

The concrete example of the represented compound of general formula (TA-4) is below shown, but is not limited to these examples.These compounds can be used alone or are used in combination two or more.

[changing 64]

As thermal acid generator and preferred acid imide sulfonate compound can be enumerated the compound of following general formula.

[changing 65]

In formula, C ₁(carbon atom) and C ₂between (carbon atom) through singly-bound or two key and bond, R ₅₁or R ₅₂can be identical also can be different, represent any of following (1)～(4),

(1) independent is respectively hydrogen atom, alkyl, naphthenic base, aryl, (2) and C ₁, C ₂form and can contain one or more heteroatomic monocycles or encircle more together,

(3) form and contain C ₁and C ₂the aromatic rings of condensation, (4) represent to contain the imido residue of N-sulfonyloxy.

R ₅₃represent alkyl, halogenated alkyl, cyclic alkyl, thiazolinyl, can there is substituent aryl, can there is substituent aralkyl or camphoryl.

R in general formula (TA-5) ₅₁and R ₅₂while being equivalent to the situation of (1), the carbon number that alkyl can be enumerated methyl, ethyl, propyl group, isopropyl, normal-butyl, the second butyl, tributyl and so on is the alkyl of 1～4.It is the base of 3～8 that naphthenic base can be enumerated the carbon numbers such as cyclopropyl, cyclopentyl, cyclohexyl, ring octyl group.The carbon number that aryl can be enumerated phenyl, tolyl, xylyl, trimethylphenyl, naphthyl and so on is the base of 6～14.At R ₅₁and R ₅₂while being equivalent to the situation of (2), for example, can enumerate the part-structure as following.

[changing 66]

At R ₅₁and R ₅₂while being equivalent to the situation of (3), for example, can enumerate the part-structure as following.

[changing 67]

At R ₅₁and R ₅₂while being equivalent to the situation of (4), can enumerate: at least two N-sulfonyloxy acid imide residues of what is called are at the R with the part-structure of above-mentioned (1)～(3) ₅₁and R ₅₂part through singly-bound or as following as the divalent organic base bond person of forming.Wherein, following concatenating group can be used alone or is used in combination two or more.

[divalent organic base] :-O-,-S-,-SO-,-SO ₂-,-NH-,-CO-,-CO ₂-,-NHSO ₂-,-NHCO-,-NHCO ₂-,

[changing 68]

(R ₅₅and R ₅₆represent respectively hydrogen atom or methyl.M is 1～4 integer).

R ₅₃alkyl can to enumerate carbon number be the 1～straight chain of 20 or the alkyl of branch.Being preferably carbon number is the 1～straight chain of 16 or the alkyl of branch, and then to be preferably carbon number be the base of 1～12.When carbon number is the situation of more than 21 alkyl, therefore sensitivity, parsing power (resolving power) reduce not good enough.Halogenated alkyl can be enumerated the base that one or more hydrogen atom of abovementioned alkyl forms through halogenation.The halogen atom replacing can be enumerated fluorine atom, chlorine atom, bromine atoms, iodine atom.Be preferably fluorine atom, chlorine atom, bromine atoms, be particularly preferably fluorine atom.Wherein, the halogen atom replacing also can be multiple in every a part.Cyclic alkyl can be enumerated: the carbon numbers such as cyclopropyl, cyclopentyl, cyclohexyl, ring octyl group are the polycyclic substituting groups such as the naphthenic base of 3～12 or norborny, adamantyl, three ring decyls.It is the 2～straight chain of 20 or the thiazolinyl of branch that thiazolinyl can be enumerated carbon number.Being preferably carbon number is the 2～straight chain of 16 or the thiazolinyl of branch, and then to be preferably carbon number be the base of 2～12.When carbon number is the situation of more than 21 thiazolinyls, sensitivity, parsing power reduce, therefore not good enough.

R ₅₃aryl can enumerate phenyl, naphthyl, aralkyl can be enumerated benzyl.The substituting group of aryl and aralkyl can be enumerated: the low alkyl groups such as methyl, ethyl, propyl group, isopropyl, tributyl; the naphthenic base such as cyclopentyl, cyclohexyl; the aryl such as phenyl, toluyl groups, xylyl, trimethylphenyl; the lower alkoxies such as methoxyl, ethoxy, propoxyl group, isopropoxy, the second butoxy, the 3rd butoxy; the thiazolinyls such as vinyl, allyl, propenyl, butenyl group; the acyl group such as formoxyl, acetyl group; hydroxyl; carboxyl; cyano group; nitro, the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom.Be preferably the low alkyl groups such as methyl, ethyl, propyl group, isopropyl, tributyl; cyclohexyl; phenyl, toluyl groups; the lower alkoxies such as methoxyl, ethoxy, propoxyl group, isopropoxy, the second butoxy, the 3rd butoxy; cyano group; nitro, the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom.Moreover the substituting group on aryl, aralkyl also can be two or more.

The concrete example of these compounds is below shown, but is not limited to these examples.

[changing 69]

[changing 70]

As thermal acid generator and preferred oxime sulfonates compound can be enumerated the compound of following general formula.

[changing 71]

In above-mentioned general formula (TA-6), R ₆₁and R ₆₂what represent that carbon number is 1～16 has substituent alkyl, thiazolinyl, alkynyl, naphthenic base, cycloalkenyl group, can have substituent aryl, heteroaryl, cyano group.In addition, R ₆₁and R ₆₂also can be 2～8 via carbon number have substituent alkylidene chain, alkenylene chain, alkynylene chain or comprise can there is substituent phenylene, the coupling chain of arlydene, sub-thienyl ,-O-,-S-,-N-,-CO-, with the R of the represented compound of other general formula (TA-6) ₆₁or R ₆₂bond.That is, the represented compound of general formula (TA-6) also comprises the compound via coupling chain with 2 or 3 oxime sulfonates structures.

R ₆₃represent that carbon number is 1～16 having substituent alkyl, naphthenic base, can have substituent aryl.

R ₆₁～R ₆₃carbon number be that the alkyl of 1～16 can be enumerated: the alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, tributyl, the 3rd amyl group, n-hexyl, n-octyl, iso-octyl, positive decyl, undecyl, dodecyl, cetyl, trifluoromethyl, perfluoro propyl, perfluoro butyl, perfluor-tributyl, perfluoro capryl, perfluor undecyl, 1,1-bis trifluoromethyl ethyl etc.

R ₆₁and R ₆₂thiazolinyl can enumerate: allyl, methacrylic (methallyl), vinyl, methacrylic (methylallyl), 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadiene base, 5-hexenyl, 2-oxa--3-pentenyl, ten-pentenyl, 7-octenyl etc.

R ₆₁and R ₆₂alkynyl can enumerate: ethinyl, propargyl, 2-butynyl, 4-hexin base, 2-octyne base, phenylene-ethynylene, cyclohexyl-acetylene base etc.

R ₆₁～R ₆₃naphthenic base can enumerate: the carbon number can with substituent cyclopropyl, cyclopentyl, cyclohexyl and so on is the base of 3～8.

R ₆₁and R ₆₂cycloalkenyl group can enumerate: cyclobutane base, cyclohexenyl group, cyclopentadienyl group, dicyclo [4.2.4] 12 carbon-3,7-diene-5-base etc.

R ₆₁～R ₆₃aryl can enumerate: the carbon number can with substituent phenyl, tolyl, methoxyphenyl, naphthyl and so on is the base of 6～14.

Above-mentioned substituting group can be enumerated: the base shown in alkyl, naphthenic base, alkoxy, halogen atom (fluorine atom, chlorine atom, iodine atom), cyano group, hydroxyl, carboxyl, nitro, aryloxy group, alkylthio group, aralkyl, following general formula (1A) etc.

Herein, alkyl, naphthenic base and above-mentioned cited person are identical meanings.Alkoxy can be enumerated: the carbon number of methoxyl, ethoxy, hydroxyl-oxethyl, propoxyl group, n-butoxy, isobutoxy, the second butoxy, the 3rd butoxy and so on is the base of 1～4.Aralkyl can be enumerated: benzyl, naphthyl methyl, furyl, thienyl etc.

[changing 72]

In above-mentioned formula, R ₆₁and R ₆₂with the R in above-mentioned general formula (TA-6) ₆₁and R ₆₂for identical meanings.

The concrete example of the represented compound of general formula (TA-6) is below shown, but the present invention is not limited to these examples.

[changing 73]

[changing 74]

As thermal acid generator and preferred oxime sulfonates is that acid producing agent can be enumerated the compound with the represented base of at least one following general formula (TA-7).

[changing 75]

(in formula (TA-7), R ^70aand R ^70bindependently represent respectively organic group)

R ^70aand R ^70borganic group be the base that contains carbon atom, also can contain the atom (such as hydrogen atom, oxygen atom, nitrogen-atoms, sulphur atom, halogen atom (fluorine atom, chlorine atom etc.) etc.) beyond carbon atom.

R ^70aorganic group be preferably the alkyl or aryl of straight chain, branch or ring-type.These alkyl, aryl also can have substituting group.There is no particular restriction for this substituting group, such as enumerating alkyl of straight chain, branch or ring-type that fluorine atom, carbon number are 1～6 etc.Herein, so-called " thering is substituting group ", part or all of hydrogen atom that refers to alkyl or aryl is substituted base and replaces.

It is 1～20 that alkyl is preferably carbon number, and more preferably carbon number is 1～10, and then to be preferably carbon number be 1～8, and being particularly preferably carbon number is 1～6, and most preferably being carbon number is 1～4.Alkyl is particularly preferably through local or complete fully halogenated alkyl (being sometimes referred to as below halogenated alkyl).Moreover the so-called alkyl through local halogenation, refers to that a part for hydrogen atom is through the alkyl of halogen atom replacement, so-called through complete fully halogenated alkyl, refers to the alkyl that hydrogen atom all replaces through halogen atom.Halogen atom can be enumerated fluorine atom, chlorine atom, bromine atoms, iodine atom etc., is particularly preferably fluorine atom.That is, halogenated alkyl is preferably fluorinated alkyl.

It is 4～20 that aryl is preferably carbon number, and more preferably carbon number is 4～10, and most preferably being carbon number is 6～10.Aryl is particularly preferably through local or complete fully halogenated aryl.Moreover the so-called aryl through local halogenation, refers to that a part for hydrogen atom is through the aryl of halogen atom replacement, so-called through complete fully halogenated aryl, refers to the aryl that hydrogen atom all replaces through halogen atom.

R ^70abe particularly preferably that not have substituent carbon number be the fluorinated alkyl that 1～4 alkyl or carbon number are 1～4.

R ^70borganic group be preferably alkyl, aryl or the cyano group of straight chain, branch or ring-type.R ^70balkyl, aryl can enumerate and above-mentioned R ^70ain the identical base of alkyl, aryl enumerated.

R ^70bbeing particularly preferably cyano group, not having substituent carbon number is the fluorinated alkyl that 1～8 alkyl or carbon number are 1～8.

With regard to regard to the high aspect of the sour generation efficiency of the irradiation of electron beam, oxime sulfonates is that acid producing agent can preferably be used following general formula (TA-7a) or the represented compound of general formula (TA-7b).

[changing 76]

[in formula (TA-7a), m ' expression 0 or 1; X represents 1 or 2; R ₇₁phenyl, heteroaryl that alkyl that expression can be 1～12 through carbon number replaces, or more represent that carbon number is 2～6 alkoxy carbonyl, phenyloxycarbonyl, CN (cyano group) during the situation that is 0 at m '; R ₇₂with R ₇₁for identical meanings; R ₇₃' at X, be to represent that carbon number is 1～18 alkyl at 1 o'clock, at X, be to represent that carbon number is 2～12 alkylidene, phenylene at 2 o'clock; R ₇₄, R ₇₅independent represent-S-of alkyl A ,-O-, the-N (R that represents that hydrogen atom, halogen atom, carbon number are 1～6 ₇₆)-.R ₇₆represent alkyl, aryl or aralkyl]

[changing 77]

[in formula (TA-7b), R ₇₁the alkylidene that ' expression carbon number is 2～12; R ₇₂, R ₇₄, R ₇₅, A and above-mentioned be identical meanings; R ₇₃represent the alkyl that carbon number is 1～18]

Above-claimed cpd is particularly preferably the following oxime sulfonates that contains thiol-ene.

[changing 78]

The general formula of preferred nitrobenzyl sulfonate esters can be enumerated the represented compound of general formula (TA-9).

[changing 79]

(Z of this formula is selected from alkyl, aryl, alkylaryl, the alkyl replacing through halogen, the aryl replacing through halogen, the alkylaryl replacing through halogen, the aryl replacing through nitro, the alkylaryl replacing through nitro, has the aryl of nitro substituent and halogenic substituent, has the alkylaryl of nitro substituent and halogenic substituent and contain formula C ₆h ₄5O ₃cHR ' C ₆h _4-mq _m(NO) ₂base, R represents hydrogen atom or methyl, the aryl that R ' is selected from hydrogen atom, methyl and replaces through nitro, each Q is independently selected from alkyl, oxyl, NO ₂, halogen atom and organic silica-based, the value of m is 0,1 or 2, wherein, Q non-acid base)

About the concrete example of the represented compound of general formula (TA-9), for example, can enumerate following compound.

[changing 80]

In addition, also can use sulphonic acid ester.

For example can enumerate the represented sulphonic acid ester of following general formula (TA-1).

R′-SO ₂-O-R″(TA-1)

In above-mentioned formula, R ' and R " respectively independent expression can there is alkyl that substituent carbon number is 1～10 straight chain or branch or ring-type, maybe can there is the aryl that the carbon number of replacement is 6～20.Substituting group can be enumerated straight chain that hydroxyl, halogen atom, cyano group, vinyl, ethinyl carbon number are 1～10 or the alkyl of ring-type.

The preferred concrete example of this sulphonic acid ester can be enumerated following compound.

[changing 81]

With regard to stable on heating aspect, sulphonic acid ester is the represented compound of following general formula (TA-2) more preferably.

The molecular weight of sulphonic acid ester is generally 230～1000, is preferably 230～800.

[changing 82]

A represents the concatenating group of h valency.

R ₀represent alkyl, aryl, aralkyl or cyclic alkyl.

R ₀' expression hydrogen atom, alkyl or aralkyl.

H represents 2～8 integer.

As the concatenating group of the h valency of A such as enumerating: alkylidene (such as methylene, ethylidene, propylidene etc.), cycloalkylidene (cyclohexylidene, cyclopentylene etc.), arlydene (1,2-phenylene, 1,3-phenylene, Isosorbide-5-Nitrae-phenylene, naphthylene etc.), hydrogen atom is arbitrarily removed to h-2 the base forming in ether, carbonyl, ester group, amide group and bivalent radical that these bases are combined.

Carbon number as the concatenating group of the h valency of A is generally 1～15, is preferably 1～10, and more preferably 1～6.

R ₀and R ₀' alkyl to be generally carbon number be 1～20 alkyl, be preferably carbon number and be 1～15 alkyl, and then to be preferably carbon number be 1～8 alkyl.Specifically can enumerate methyl, ethyl, propyl group, butyl, hexyl, octyl group etc.

R ₀and R ₀' aralkyl to be generally carbon number be 7～25 aralkyl, be preferably carbon number and be 7～20 aralkyl, and then to be preferably carbon number be 7～15 aralkyl.Specifically can enumerate benzyl, toluyl ylmethyl, trimethylphenyl methyl, phenethyl etc.

R ₀cyclic alkyl to be generally carbon number be 3～20 cyclic alkyl, be preferably carbon number and be 4～20 cyclic alkyl, and then to be preferably carbon number be 5～15 cyclic alkyl.Specifically can enumerate cyclopentyl, cyclohexyl, norborny, camphoryl etc.

Concatenating group as A also can have more substituting group, and substituting group can be enumerated: (alkyl that carbon number is 1～10 is particularly methyl to alkyl, ethyl, propyl group, butyl, hexyl, octyl group etc.), (aralkyl that carbon number is 7～15 is particularly benzyl to aralkyl, toluyl ylmethyl, trimethylphenyl methyl, phenethyl etc.), (aryl that carbon number is 6～10 is particularly phenyl to aryl, toluyl groups, xylyl, trimethylphenyl, naphthyl etc.), (alkoxy can be straight chain to alkoxy, branch, any of ring-type, is the alkoxy that carbon number is 1～10, is particularly methoxyl, ethoxy, straight chain or branch's propoxyl group, straight chain or branch's butoxy, straight chain or branch's amoxy, cyclopentyloxy, cyclohexyloxy etc.), (aryloxy group that carbon number is 6～10 is particularly phenoxy group to aryloxy group, toloxyl, 1-naphthoxy etc.), alkylthio group (can be straight chain, branch, any of ring-type, is the alkylthio group that carbon number is 1～10, is particularly methyl mercapto, ethylmercapto group, straight chain or branch's rosickyite base, encircle penta sulfenyl, hexamethylene sulfenyl), (arylthio that carbon number is 6～10 is particularly thiophenyl to arylthio, toluyl sulfenyl, 1-naphthalene sulfenyl etc.), (acyloxy that carbon number is 2～10 is particularly acetoxyl group to acyloxy, propionyloxy, benzoyloxy etc.), (alkoxy carbonyl that carbon number is 1～10 is particularly methoxycarbonyl to alkoxy carbonyl, ethoxy carbonyl, straight chain or branch's propoxycarbonyl, cyclopentyloxy carbonyl, cyclohexyloxy carbonyl etc.).

In general formula (2), R ₀be preferably alkyl and aryl.R ₀' alkyl that to be preferably hydrogen atom and carbon number be 1～6, is preferably hydrogen atom, methyl and ethyl, most preferably is hydrogen atom.

The particular compound that sulphonic acid ester of the present invention can be listed below as stating is example, but is not limited to this.

[changing 83]

[changing 84]

Sulphonic acid ester of the present invention can be used commercially available product, also can use by the known method person of synthesizing.Sulphonic acid ester of the present invention for example can synthesize in the following manner: under alkali condition, make sulfonic acid chloride or sulphonic acid anhydride and corresponding polyol reaction.

In photosensitive polymer combination of the present invention, the total solid composition of photosensitive polymer combination of take is benchmark, and thermal acid generator's content is preferably 1 quality %～20 quality %, more preferably 3 quality %～10 quality %.

(e) compound of at least one that contains alkoxy methyl and acyloxy methyl

In composition of the present invention, also can contain following compound, at least one that this compound contains alkoxy methyl and acyloxy methyl.In low-temperature setting technique, the melting of the pattern in the time of also can preventing from hardening or thermal shrinkage.

The compound of at least one that contains alkoxy methyl and acyloxy methyl of the present invention can be enumerated following compound as representative structure, and above-claimed cpd is that alkoxy methyl or acyloxy methyl are directly replaced on aromatic series base or on the nitrogen-atoms of following urea structure, are replaced in the compound in triazine.

It is 2～5 that the alkoxy methyl that this compound has or acyloxy methyl are preferably carbon number, and being preferably carbon number is 2 or 3, and being particularly preferably carbon number is 2.

The sum of the alkoxy methyl that this compound has and acyloxy methyl is preferably 1～10, and more preferably 2～8, be particularly preferably 3～6.

The molecular weight of this compound is preferably below 1500, is preferably 180～1200.

[changing 85]

R ₁₀₀represent alkyl or acyl group.

R ₁₀₁and R ₁₀₂the independent any monovalent organic radical that represents, also bond and form ring mutually.

Alkoxy methyl or acyloxy methyl are directly replaced in the various compounds that compound on aromatic series base for example can be enumerated following general formula.

[changing 86]

In formula, X represents singly-bound or divalent organic base, each R ₁₀₄independent alkyl or acyl group, the R of representing ₁₀₃represent hydrogen atom, alkyl, thiazolinyl, aryl, aralkyl or by sour effect, base (base for example departing from by sour effect, the-C (R that produces alkali-soluble base occur to decompose ⁴) ₂cOOR ⁵represented base (R ⁴represent the alkyl that hydrogen atom or carbon number are 1～4, R ⁵the base that expression departs from by sour effect)).

R ₁₀₅independently represent respectively alkyl or alkenyl, a, b and c are independently respectively that 1～3, d is that 0～4, e is independently 0～3.

About the effect by sour, occur to decompose and produce the base of alkali-soluble base, the base departing from by sour effect ,-C (R ⁴) ₂cOOR ⁵represented base is identical with person in general formula (1).

The compound with alkoxy methyl specifically can be enumerated following structure.The compound with acyloxy methyl can be enumerated the alkoxy methyl of following compound is changed to the compound that acyloxy methyl forms.The compound in molecule with alkoxy methyl or acyloxy methyl can be enumerated as the compound as following, but is not limited to these compounds.

[changing 87]

[changing 88]

The compound of at least one that contains alkoxy methyl and acyloxy methyl can be used commercially available product, also can use by the known method person of synthesizing.

With regard to stable on heating viewpoint, be preferably alkoxy methyl or acyloxy methyl is directly replaced in the compound on aromatic rings or triazine ring.

With respect to total amount 100 mass parts of resin of the present invention, the addition of these compounds is preferably 1 mass parts～20 mass parts, more preferably 3 mass parts～15 mass parts.

The compound that (e ') contains methacryl or acryloyl group

Composition of the present invention also can contain the compound of methacryl or acryloyl group.

The compound that what is called contains methacryl or acryloyl group, refers to the compound selecting in the cohort that free acrylate, methacrylate form.These compounds are insoluble to alkaline developer, thus there is the deliquescent effect of the alkali of composite inhibiting, and suppress the film minimizing of unexposed portion, therefore form and play a role for good image.In addition, though concrete reaction mechanism is not yet grasped, in the stage of curing reaction, acryloyl group or methacryl react with the compound in composition, and the molecular weight that forms thus the composition of composition increases partly, thereby film physical property improves.Therefore, by be set as having more than 2 acryloyl group, methacryls in a part, and then be preferably the compound that 4 officials can be above, this compound can be brought into play the function of cross-linking compounds, therefore preferably.

In addition, the expose outspoken nature of optical transmission rate and cured film of take is object, more preferably contains the compound that the skeleton of acryloyl group, methacryl contains ring structure, the particularly alicyclic structures such as aromatic rings or alicyclic ring.

And then if the length (n) of the oxirane in skeleton (EO) chain, epoxypropane (PO) chain is long, film is lost outspoken nature, therefore be preferably n=1～5.

Preferred concrete example can be enumerated: the AMP-10G of a sense in NK ester (NK Ester) series that Xin Zhong village chemical industrial company manufactures, AMP-20GY, AM30G, AM90G, AM230G, ACB-3, A-BH, A-IB, A-SA, A-OC-18E, 720A, S-1800A, ISA, AM-130G, LA, M-20G, M-90G, M230G, PHE-1G, SA, CB-1, CB-3, CB-23, TOPOLENE-M, S-1800M, IB, OC-18E, S, the A-200 of two senses, A-400, A-600, A-1000, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A-B1206PE, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, BD, HD-N, NOD, IND, BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3PG, 9PG, the A-9300 of trifunctional, AT-30E, A-TMPT-3EO, A-TMPT-9EO, A-TMPT-3PO, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, TMPT, TMPT-9EO, ATM-35E more than four senses, ATM-4E, AD-TMP, AD-TMP-L, ATM-4P, A-TMMT, A-DPH.

The polyfunctional monomer that particularly preferred example can be listed below.

[changing 89]

[changing 90]

With respect to resin 100 mass parts with the represented repetitive of general formula (1), the addition that molecule of the present invention contains the compound of methacryl or acryloyl group be preferably 0.5 mass parts above, below 30 mass parts.And then more than being preferably 1 mass parts, below 20 mass parts, more than being particularly preferably 2 mass parts, below 15 mass parts.By addition being set as to certain more than 0.5 mass parts, can further obtain effect of the present invention, by suitable inhibition addition, can prevent that the thermotolerance of cured film from reducing.

(f) connect airtight promoter

In positive type photosensitive organic compound of the present invention, organo-silicon compound, silane coupling agent, homogenize agent that optionally also can add to give adhesion etc. connect airtight promoter.The example of these adjuvants for example can be enumerated: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, vinyltriethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl trimethoxy silicane, to styryl trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane, urea propyl-triethoxysilicane, three (acetopyruvic acid) aluminium, acetoacetate aluminium diisopropyl ester etc.When the situation of promoter is connected airtight in use, with respect to resin 100 mass parts of the present invention, be preferably 0.1 mass parts～20 mass parts, more preferably 0.5 mass parts～10 mass parts.

(g) solvent

Solvent, as long as solubilized composition of the present invention is not particularly limited, is separated out the solid constituent of composition when being coated with in order not evaporate solvent more than necessary amount when being coated with, be preferably the solvent of 100 ℃ of above boiling points.Such as enumerating: organic solvents such as alkane glycol monoalkyl ether carboxylate, alkane glycol monoalkyl ether, lactic acid alkyl ester, alkoxypropan acid alkyl ester, annular lactone (being preferably carbon number is 4～10), the single ketones compound (being preferably carbon number is 4～10) that can contain ring, alkylene carbonates, alkoxy acetic acid Arrcostab, pyruvate alkyl esters, acid amides series solvents.

Alkane glycol monoalkyl ether carboxylate for example can preferably be enumerated: propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, propylene glycol monobutyl ether acetic acid esters, propylene glycol monomethyl ether propionate, dihydroxypropane single-ether propionic ester, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate.

Alkane glycol monoalkyl ether for example can preferably be enumerated: propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether.

Lactic acid alkyl ester for example can preferably be enumerated: methyl lactate, ethyl lactate, propyl lactate, butyl lactate.

Alkoxypropan acid alkyl ester for example can preferably be enumerated: 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl esters, 3-methoxy propyl acetoacetic ester.

Annular lactone for example can preferably be enumerated: beta-propiolactone, beta-butyrolactone, gamma-butyrolacton, Alpha-Methyl-gamma-butyrolacton, Beta-methyl-gamma-butyrolacton, gamma-valerolactone, γ-hexalactone, γ-octalactone, Alpha-hydroxy-gamma-butyrolacton.

The single ketones compound that can contain ring for example can preferably be enumerated: 2-butanone, 3-espeleton, pinacoline (pinacolone), 2 pentanone, propione, 3-methyl-2 pentanone, 4-methyl-2 pentanone, 2-methyl-propione, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-propione, 2,2,4,4-tetramethyl-propione, methyl-n-butyl ketone, 3-hexanone, 5-methyl-3-hexanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-valerone, methyln-hexyl ketone, 3-octanone, methyl n-heptyl ketone, 3-nonanone, butyl ketone, 2-decanone, 3-decanone, 4-decanone, 5-hexene-2-ketone, 3-amylene-2-ketone, cyclopentanone, 2-methyl-cyclopentanone, 3-methyl-cyclopentanone, 2,2-cyclopentanone dimethyl, 2,4,4-trimethyl cyclopentanone, cyclohexanone, 3-methyl cyclohexanone, 4-methyl cyclohexanone, 4-ethyl cyclohexanone, 2,2-dimethylcyclohexanon, 2,6-dimethylcyclohexanon, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methyl cycloheptanone, 3-methyl cycloheptanone.

Alkylene carbonates for example can preferably be enumerated: propylene carbonate, vinylene carbonate, ethylene carbonate, butylene carbonate.

Alkoxy acetic acid Arrcostab for example can preferably be enumerated: acetic acid-2-methoxy-ethyl ester, acetic acid-2-ethoxy-ethyl ester, acetic acid-2-(2-ethoxy ethoxy) ethyl ester, acetic acid-3-methoxyl-3-methyl butyl ester, acetic acid-1-methoxyl-2-propyl ester.

Pyruvate alkyl esters for example can preferably be enumerated: methyl pyruvate, ethyl pyruvate, Propyl pyruvate.

Acid amides series solvent can preferably be enumerated: and DMF, DMA, METHYLPYRROLIDONE, DMI (1,3-dimethyl-2-imidazolidinone).

In addition, can preferably enumerate dimethyl sulfoxide (DMSO), sulfolane.

In above-mentioned, more suitable solvent can be enumerated: 1-METHYLPYRROLIDONE (NMP), gamma-butyrolacton (GBL), N, N-dimethyl acetamide (DMAc), 1,3-dimethyl-2-imidazolinone (DMI), DMF (DMF), cyclopentanone, cyclohexanone, cycloheptanone etc.And then be preferably gamma-butyrolacton and 1-METHYLPYRROLIDONE, cyclopentanone, cyclohexanone.

These solvents can be used alone also can mix use two or more.

Total solid constituent concentration in photosensitive polymer combination of the present invention is generally 10 quality %～40 quality %, 10 quality %～30 quality % more preferably, and then be preferably 15 quality %～30 quality %.

[relief pattern manufacture method]

As manufacture the method for relief pattern with photosensitive polymer combination of the present invention, can form the relief pattern through sclerosis by following operation: (a) photosensitive polymer combination of the present invention is coated and on suitable substrate, formed photosensitive film, (b) this substrate through coating is toasted to (prebake conditions), (c) utilize active ray or radioactive ray to expose, (d) utilize water developer to develop, (e) hardens then.In part at above-mentioned be coated with photosensitive film through exposing, in above-mentioned general formula (1)-CO ₂r ³by sour effect, decomposition occurs and produce alkali-soluble base, the mode of removing in order to use alkaline developer is developed, therefore can obtain the relief pattern through sclerosis of eurymeric.

Also can the substrate through coating, exposure first be developed, then at high temperature toast (postexposure bake).In addition, also can before sclerosis, carry out drip washing to the substrate through developing.

So, can be by photosensitive polymer combination of the present invention the mode that becomes predetermined thickness (for example 0.1 μ m～30 μ m) of thickness after with heat hardening coat on semiconductor element, carry out prebake conditions, exposure, development, heat hardening and manufacture semiconductor device.

Below, to manufacturing the method for relief pattern, be described in more detail.

Photosensitive polymer combination of the present invention is coated on suitable substrate.Substrate is for example semiconductor material or ceramic base material, glass, metal or the plastics of silicon wafer and so on.In coating process, there are spraying coating, rotary coating, copy printing, roller coat cloth, screen painting, extrusion coated, meniscus coating, curtain type coating and dip coated, but are not limited to these methods.

This coated film is toasted to a few minutes to half an hour at the temperature of approximately 70 ℃～150 ℃, so that evaporate residual solvent.Then, the film of gained is carried out to the exposure of active ray or radioactive ray across shade.Active ray or radioactive ray can be used X ray, electron beam, ultraviolet ray, luminous ray etc.Most preferred radioactive ray are for having the radioactive ray of the wavelength of 365nm (i ray) or 436nm (g ray).

After being preferably the exposure under active ray or radioactive ray, the substrate through exposure is heated at the temperature of approximately 70 ℃～150 ℃.Conventionally with the temperature heating of tens seconds～a few minutes to be scheduled to.The method is called as postexposure bake.

By this postexposure bake, as following flow process, by the poly amic acid ester generation polyamic acid of above-mentioned general formula (1).

[changing 91]

Then, can utilize water developer to develop to this coated film, obtain relief pattern.Water developer can be enumerated: the alkaline solution of inorganic base (for example potassium hydroxide, NaOH, ammoniacal liquor), primary amine (for example ethamine, n-propylamine), secondary amine (for example diethylamine, di-n-propylamine), tertiary amine (for example triethylamine), hydramine (for example triethanolamine), quarternary ammonium salt (for example tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide) and these potpourri and so on.Most preferred developer contains tetramethyl ammonium hydroxide.And then, also can in developer, add the interfacial agent of suitable amount.Development can be implemented by dipping, spraying, stirring or other same developing methods.

Optionally different, relief pattern also can be used deionized water to rinse.Then,, in order to obtain the final pattern film that thermotolerance is high, as following flow process, by being carried out to heat hardening, relief pattern generates polyimide by poly amic acid ester.In order to obtain the polyimide that thermotolerance is high, the glass transition temperature T that sclerosis is preferably at polymkeric substance _gmore than toast.Heat hardening temperature is preferably approximately 200 ℃～400 ℃, is particularly preferably 250 ℃～400 ℃.

[changing 92]

Embodiment

Below, by embodiment, the present invention is illustrated, but the present invention is not limited to these embodiment.

[gel permeation chromatography (Gel Permeation Chromatography, GPC) condition determination]

It is to carry out in the following manner that following GPC measures: by HPC-8220GPC (eastern Cao manufactures), protection tubing string: TSK guard column SuperAW-H, tubing string: tri-series connection of TSK gel Super AWM-H; tubing string temperature is 50 ℃; injecting sample solution concentration is the METHYLPYRROLIDONE solution 20 μ l of 0.5 quality %, makes the METHYLPYRROLIDONE solution as stripping solvent (contain LiBr (10mM) and H ₃pO ₄(10mM)) with the traffic flow of per minute 0.35ml, utilize refractive index (Refractive Index, RI) pick-up unit test samples peak value.Mw and Mn utilize with the calibration curve that polystyrene standard is made to calculate.

The synthesis example > of < resin

[P-1's is synthetic]

Synthesizing of polyamic acid

In possessing the 5000mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 123.42g, after being dissolved in NMP (METHYLPYRROLIDONE) 2399.4g, add 3,3 ', 4,4 '-N-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 300.00g.At 60 ℃, stir 4 hours, till placement is cooled to room temperature (25 ℃) thereafter.Then add phthalic anhydride 30.27g, at room temperature stir 10 hours and obtain water white polyamic acid solution.If utilize GPC to analyze the solution of gained, Mw=1.68 * 10 ⁴, Mn=0.62 * 10 ⁴, Mw/Mn=2.71.

Synthesizing of poly amic acid ester

This polyamic acid solution 132.01g is added to and possesses thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP111.0g and carry out coolingly, at 0 ℃ of following chloromethyl methyl ether 12.56g that adds, then add DIPEA 16.12g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1175g, will separates out solid leaching, dry, obtain object (resin P-1) 24.6g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.00 * 10 ⁴, Mw/Mn=1.91.Dissolution of solid is also measured in deuterated dimethyl sulfoxide (Dimethyl Sulfoxide, DMSO) ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-2's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-1.This polyamic acid solution 132.01g is added to and possesses thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP111.0g and carry out coolingly, at 0 ℃ of following chloromethyl methyl ether 5.02g that adds, then add DIPEA 8.06g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1175g, will separates out solid leaching, dry, obtain object (resin P-2) 19.3g of white solid.If utilize GPC to analyze the resin of gained, Mw=1.88 * 10 ⁴, Mw/Mn=1.68.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 72%.

[P-3's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-1.This polyamic acid solution 142.26g is added to and possesses thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP70.37g and carry out coolingly, at 0 ℃ of following chloromethyl ether 15.91g that adds, then add DIPEA 17.39g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1267g, will separates out solid leaching, dry, obtain object (resin P-3) 23.6g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.09 * 10 ⁴, Mw/Mn=1.73.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 96%.

[P-7's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-1.This polyamic acid solution 132.01g is added to possess thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP111.0g and carry out cooling, at 0 ℃ of following chloromethyl hexamethylene ether 23.18g that adds, then add DIPEA 16.12g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1175g, will separates out solid leaching, dry, obtain object (resin P-7) 24.8g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.36 * 10 ⁴, Mw/Mn=1.72.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-8's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-1.This polyamic acid solution 132.01g is added to and possesses thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP111.0g and carry out coolingly, at 0 ℃ of following chloromethyl hexamethylene ether 9.27g that adds, then add DIPEA 8.06g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1175g, will separates out solid leaching, dry, obtain object (resin P-8) 20.2g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.13 * 10 ⁴, Mw/Mn=1.59.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 64%.

[P-11's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-1.This polyamic acid solution 106.30g is added to possess thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP52.59g and carry out cooling, at 0 ℃ of following 2-(chlorine methoxyl) ethyl trimethyl silane 20.96g that adds, then add DIPEA 13.00g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 947g, will separates out solid leaching, dry, obtain object (resin P-11) 13.5g of white solid.If utilize GPC to analyze the resin of gained, Mw=1.58 * 10 ⁴, Mw/Mn=1.55.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 73%.

[P-16's is synthetic]

Paraldehyde 48.11g, cyclohexane ethanol 140.0g, 10-camphorsulfonic acid 1.27g are added in hexane 150g, utilize Dien-Rodney Stark (Dean-Stark) device to reflux 5 hours.Solution is sequentially cleaned 2 times with saturated sodium bicarbonate solution, with water, clean 2 times, by sodium sulphate, organic layer is dry, under reduced pressure concentrate and acquisition clear solution 157g.Add therein acetyl chloride 34.3g and at 50 ℃, react after 5 hours, under reduced pressure concentrating and acquisition transparency liquid 178g.Be dissolved in deuterochloroform and measure ¹h-NMR spectrum, the containing ratio of learning cyclohexyl ethyl-1-dichloroethyl ether is 31 quality %.

Similarly carry out the synthetic of polyamic acid with P-1, this polyamic acid solution 105.61g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP52.23g and carry out cooling, at 0 ℃ of following solution 76.75g that adds above-mentioned 31 quality %, then add DIPEA 26.87g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in acetonitrile 940g, will separates out solid leaching, dry, obtain object (resin P-16) 16.5g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.29 * 10 ⁴, Mw/Mn=1.75.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 69%.

[P-19's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-1, this polyamic acid solution 106.30g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP52.59g, sequentially add (2-phenoxy group ethyl) vinethene 20.64g, 10-camphorsulfonic acid 0.97g.At 25 ℃, react after 5 hours, reactant liquor is added in acetonitrile 947g, will separate out solid leaching, dry, obtain object (resin P-19) 18.9g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.50 * 10 ⁴, Mw/Mn=1.71.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-22's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-1, this polyamic acid solution 105.59g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP52.23g, sequentially add (1-(4-the trioctylphosphine-phenoxy group)-2-ethyleneoxy-ethane 34.43g, 10-camphorsulfonic acid 0.96g.At 25 ℃, react after 5 hours, reactant liquor is added in acetonitrile 940g, will separate out solid leaching, dry, obtain object (resin P-22) 22.1g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.84 * 10 ⁴, Mw/Mn=1.71.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-26's is synthetic]

Ethylene glycol list vinethene 24.93g, NSC 87419 35.42g are added in dehydration ethyl acetate 150ml, at 70 ℃, stir 6 hours.Under reduced pressure concentrated, carry out cooling and make crystallization.Crystallization is filtered, with cold hexane drip washing, obtain the vinethene 37.8g as the following structure of white, needle-shaped crystals.

[changing 93]

Similarly carry out the synthetic of polyamic acid with P-1, this polyamic acid solution 79.19g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP39.18g, sequentially add above-mentioned vinethene 19.92g, 10-camphorsulfonic acid 0.72g.At 25 ℃, react after 5 hours, reactant liquor is added in acetonitrile 705g, will separate out solid leaching, dry, obtain object (resin P-26) 15.1g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.62 * 10 ⁴, Mw/Mn=1.76.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-27's is synthetic]

Ethylene glycol list vinethene 29.00g, phenyl isocyanate 39.20g are added in dehydration ethyl acetate 150ml, at 70 ℃, stir 6 hours.Under reduced pressure concentrated (100 ℃, 0.1kPa), the vinethene 60.2g of the following structure of acquisition oily.

[changing 94]

Similarly carry out the synthetic of polyamic acid with P-1, this polyamic acid solution 79.19g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP39.18g, sequentially add above-mentioned vinethene 19.36g, 10-camphorsulfonic acid 0.72g.At 25 ℃, react after 5 hours, reactant liquor is added in acetonitrile 705g, will separate out solid leaching, dry, obtain object (resin P-26) 17.6g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.89 * 10 ⁴, Mw/Mn=1.95.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-29's is synthetic]

In possessing the 300mL flask of thermometer, stirrer, nitrogen ingress pipe, add phenyl acetaldehyde dimethylacetal 100g, acetyl chloride 54.3g, at 50 ℃, react after 5 hours, under reduced pressure concentrate, obtain the transparency liquid of following structure.

[changing 95]

Similarly carry out the synthetic of polyamic acid with P-1, this polyamic acid solution 132.8g is added to possess thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP65.68g and carry out cooling, at 0 ℃ of above-mentioned solution 25.58g of following interpolation, then add DIPEA 23.25g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1182g, will separates out solid leaching, dry, obtain object (resin P-29) 29.19g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.49 * 10 ⁴, Mw/Mn=1.65.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 97%.

[P-31's is synthetic]

In possessing the 2000mL flask of thermometer, stirrer, nitrogen ingress pipe, add 1-ethyl cyclopentanol 58.2g, dry THF 250ml, at-5 ℃ of following n-BuLi (2.6M hexane) 184ml that drip, at-2 ℃, stir 2 hours.Add therein 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride 50.0g at room temperature stirs 1 hour, appends NMP200ml and further at room temperature stirs 3 hours, stirs 1 hour at 50 ℃.Place cooling, utilize in watery hydrochloric acid and after, with ethyl acetate, 600ml extracts, and organic layer is sequentially cleaned 2 times with saturated aqueous common salt, with water, cleans 2 times, utilizes sodium sulphate that organic layer is dry, under reduced pressure concentrated and obtain the dicarboxylic acid 32.3g of following structure.

[changing 96]

This dicarboxylic acid 16.00g is added to possess thermometer, in the 100mL flask of stirrer, nitrogen ingress pipe, add NMP58.28g and carry out cooling, at 0 ℃, sequentially add below diphenyl (2,3-dihydro-2-thioketones base-3-benzoxazolyl) phosphate (DBOP) 27.61g, N, N-diisopropylethylamine 11.63g, anti-form-1,4-cyclohexane diamine 3.43g.0 ℃ of following stirring after 1 hour, at room temperature stir diel.Reactant liquor is added in methyl alcohol 700ml, will separates out solid leaching, and then utilize acetonitrile 1000ml slurrying again.Dissolution of solid, in NMP100ml, is added to phthalic anhydride 0.89g and at 50 ℃, stirs 1 hour.Reactant liquor is added in methyl alcohol 800ml/ water 200ml, is dried, obtain object (resin P-31) 15.6g of white solid.If utilize GPC to analyze the resin of gained, Mw=0.90 * 10 ⁴, Mw/Mn=2.03.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-33's is synthetic]

In possessing the 2000mL flask of thermometer, stirrer, nitrogen ingress pipe, add 2-ethyl-2-Buddha's warrior attendant alcohol 94.4g, dry THF 250ml, at-5 ℃ of following n-BuLi (2.6M hexane) 192ml that drip, at 5 ℃, stir 1 hour.Add therein 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride 70.0g, NMP280g at room temperature stir 2 hours, at 40 ℃, stir 1 hour.Place coolingly, after neutralizing with 1M-hydrochloric acid 600ml, utilize ethyl acetate 1000ml to extract, organic layer is sequentially cleaned 2 times with saturated charcoal saline solution, with water, clean 2 times.Add 1M-NaOH500ml, water layer is extracted, with ethyl acetate 300ml, clean.Water layer is neutralized with 1M-hydrochloric acid 500ml, and with ethyl acetate, 500ml extracts, and organic layer is sequentially cleaned 2 times with saturated charcoal saline solution, with water, cleans 2 times.Utilize sodium sulphate to be dried, under reduced pressure concentrated and obtain the dicarboxylic acid 76.4g of following structure.

[changing 97]

This dicarboxylic acid 15.00g is added to possess thermometer, in the 100mL flask of stirrer, nitrogen ingress pipe, add NMP52.69g and carry out cooling, at 0 ℃, sequentially add below diphenyl (2,3-dihydro-2-thioketones base-3-benzoxazolyl) phosphate (DBOP) 20.66g, N, N-diisopropylethylamine 8.70g, anti-form-1,4-cyclohexane diamine 2.56g.0 ℃ of following stirring after 1 hour, at room temperature stir 4 hours.Then add phthalic anhydride 0.67g and at room temperature stir 1 hour.Reactant liquor is added in methyl alcohol 1200ml, will separates out solid leaching, and then utilize methyl alcohol 1000ml slurrying again.By solid drying, obtain object (resin P-33) 14.7g of white solid.If utilize GPC to analyze the resin of gained, Mw=0.82 * 10 ⁴, Mw/Mn=1.64.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-34's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-1, this polyamic acid solution 142.3g is added to possess thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP70.38g, at 0 ℃ of following bromoacetic acid tributyl 31.32g, DIPEA 16.60g of adding.At room temperature react after 7 hours, reactant liquor is added in methyl alcohol 1267g, will separate out solid leaching, dry, obtain object (resin P-34) 34.07g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.38 * 10 ⁴, Mw/Mn=2.68.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-36's is synthetic]

In possessing the 1000mL flask of thermometer, stirrer, nitrogen ingress pipe, add bromoacetyl bromide 25g and dehydration NMP475g, the cooling one side of one side adds 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (1,8-Diazabicyclo[5.4.0] undec-7-ene, DBU) 50g.Cooling and at 10 ℃ of following 1-ethyl cyclopentanol 110.47g that add, at room temperature react thereafter 4 hours.Add water 600ml, utilize ethyl acetate 500ml extraction 2 times, organic layer is sequentially cleaned 2 times with saturated sodium bicarbonate solution, with water, clean 2 times, utilize magnesium sulfate that organic layer is dry, under reduced pressure concentrated and obtain the brown oil of following structure.

[changing 98]

Similarly carry out the synthetic of polyamic acid with P-1, this polyamic acid solution 142.3g is added to possess thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP70.38g, at 0 ℃ of following above-mentioned halogenide 37.76g, DIPEA 16.60g of adding.At room temperature react after 7 hours, reactant liquor is added in methyl alcohol 1267g, will separate out solid leaching, dry, obtain object (resin P-36) 36.97g of tawny solid.If utilize GPC to analyze the resin of gained, Mw=3.64 * 10 ⁴, Mw/Mn=2.51.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-39's is synthetic]

In possessing the 2000mL flask of thermometer, stirrer, nitrogen ingress pipe, add bromoacetyl bromide 111.9g and dehydration NMP360g, the cooling one side of one side is added DBU50.7g.At 10 ℃ of following 2-ethyl-2-Buddha's warrior attendant alcohol 40.0g that add, at room temperature react thereafter 4 hours.Add water 600ml, utilize ethyl acetate 500ml extraction 2 times, organic layer is sequentially cleaned 2 times with saturated sodium bicarbonate solution, with water, clean 2 times, utilize magnesium sulfate that organic layer is dry, under reduced pressure concentrated and obtain the brown oil of following structure.

[changing 99]

Similarly carry out the synthetic of polyamic acid with P-1, this polyamic acid solution 133.10g is added to possess thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP65.87g, at 0 ℃ of following above-mentioned halogenide 36.46g, DIPEA 15.65g of adding.At room temperature react after 8 hours, reactant liquor is added in methyl alcohol 1186g, will separate out solid leaching, dry, obtain object (resin P-39) 41.21g of tawny solid.If utilize GPC to analyze the resin of gained, Mw=3.97 * 10 ⁴, Mw/Mn=2.59.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-41's is synthetic]

Synthesizing of polyamic acid

In possessing the 5000mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 64.04g, after being dissolved in NMP (METHYLPYRROLIDONE) 2427.2g, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 275.00g.Till stirring at 60 ℃ 4 hours and place and being cooled to room temperature.Then, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 89.29g also stirs 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 27.69g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=1.88 * 10 ⁴, Mn=0.74 * 10 ⁴, Mw/Mn=2.55.

Synthesizing of poly amic acid ester

This polyamic acid solution 132.20g is added to and possesses thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP65.47g and carry out coolingly, at 0 ℃ of following chloromethyl methyl ether 11.39g that adds, then add DIPEA 14.62g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1178g, will separates out solid leaching, dry, obtain object (resin P-41) 25.9g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.45 * 10 ⁴, Mw/Mn=1.68.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-42's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-41.This polyamic acid solution 132.20g is added to and possesses thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP65.47g and carry out coolingly, at 0 ℃ of following chloromethyl methyl ether 3.80g that adds, then add DIPEA 6.09g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1178g, will separates out solid leaching, dry, obtain object (resin P-42) 18.8g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.20 * 10 ⁴, Mw/Mn=1.58.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 52%.

[P-45's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-41.This polyamic acid solution 136.30g is added to possess thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP67.49g and carry out cooling, at 0 ℃ of following chloromethyl Octyl Ether 24.87g that adds, then add DIPEA 14.39g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1215g, will separates out solid leaching, dry, obtain object (resin P-45) 32.1g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.83 * 10 ⁴, Mw/Mn=1.76.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 99%.

[P-47's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-41.This polyamic acid solution 146.80g is added to possess thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP72.69g and carry out cooling, at 0 ℃ of following chloromethyl hexamethylene ether 22.28g that adds, then add DIPEA 19.37g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1308g, will separates out solid leaching, dry, obtain object (resin P-47) 31.8g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.50 * 10 ⁴, Mw/Mn=1.85.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-49's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-41.This polyamic acid solution 157.30g is added to and possesses thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP77.88g and carry out coolingly, at 0 ℃ of following chloromethyl hexamethylene ether 9.55g that adds, then add DIPEA 8.30g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1402g, will separates out solid leaching, dry, obtain object (resin P-49) 26.19g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.22 * 10 ⁴, Mw/Mn=1.94.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 63%.

[P-50's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-41.This polyamic acid solution 132.20g is added to and possesses thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP65.47g and carry out coolingly, at 0 ℃ of following chloromethyl benzyl oxide 22.15g that adds, then add DIPEA 14.62g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1178g, will separates out solid leaching, dry, obtain object (resin P-50) 26.1g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.59 * 10 ⁴, Mw/Mn=1.83.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-52's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-41.This polyamic acid solution 117.51g is added to possess thermometer, in the 500mL flask of stirrer, nitrogen ingress pipe, add NMP58.19g and carry out cooling, at 0 ℃ of following 2-methoxy ethoxy methyl chloride 15.66g that adds, then add DIPEA 13.00g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1047g, will separates out solid leaching, dry, obtain object (resin P-52) 20.5g of white solid.If utilize GPC to analyze the resin of gained, Mw=3.02 * 10 ⁴, Mw/Mn=1.59.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-55's is synthetic]

2-chloroethyl vinyl ether 106.55g is added in first sodium oxide molybdena 28% methanol solution 385.86g, refluxes 12 hours.Add hexane 200ml, solution is sequentially cleaned 3 times with saturated aqueous common salt, with water, clean 2 times, by sodium sulphate, organic layer is dry, under reduced pressure concentrated and obtain (2-methoxy ethyl) vinethene as colorless transparent oil.

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 88.13g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP74.20g, sequentially add above-mentioned vinethene 9.63g, 10-camphorsulfonic acid 0.73g.At 25 ℃, react after 5 hours, reactant liquor is added in acetonitrile 786g, will separate out solid leaching, dry, obtain object (resin P-55) 12.6g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.96 * 10 ⁴, Mw/Mn=1.82.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-74's is synthetic]

In possessing the 300mL flask of thermometer, stirrer, nitrogen ingress pipe, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 5.61g and anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 4.27g, after being dissolved in METHYLPYRROLIDONE 132.24g, under ice bath is cooling, at 2 ℃, add pyromellitic dianhydride 6.40g and (1R, 2S, 4S, 5R)-cyclohexane tetracarboxylic dianhydride (manufacture, PMDA-HS) 7.06g by rock paddy gas (thigh).At 4 ℃, react 1 hour, then at 25 ℃, react after 24 hours, add phthalic anhydride 1.77g, at room temperature stir 2 hours.In this polyamic acid solution, add NMP77.79g, sequentially add (2-methoxy ethyl) vinethene 20.469g, 10-camphorsulfonic acid 1.55g.At 25 ℃, react after 5 hours, reactant liquor is added in acetonitrile 1400g, will separate out solid leaching, dry, obtain object (resin P-74) 31.6g of white solid.If utilize GPC to analyze the resin of gained, Mw=3.26 * 10 ⁴, Mw/Mn=1.90.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-93's is synthetic]

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 6.85g, after being dissolved in METHYLPYRROLIDONE 182.71g, at room temperature add (1R, 2S, 4S, 5R)-cyclohexane tetracarboxylic dianhydride (manufacture, PMDA-HS) 13.45g by rock paddy gas (thigh).At room temperature react 1 hour, then at 60 ℃, react 4 hours.If utilize GPC to analyze the solution of gained, Mw=5.53 * 10 ⁴, Mn=2.71 * 10 ⁴, Mw/Mn=2.04.In this solution, add phthalic anhydride 0.89g, at room temperature stir after 2 hours coolingly, at 0 ℃ of following chloromethyl methyl ether 15.22g that adds, then add DIPEA 19.54g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1218g, will separates out solid leaching, dry, obtain object (resin P-93) 26.1g of white solid.If utilize GPC to analyze the resin of gained, Mw=6.26 * 10 ⁴, Mw/Mn=2.11.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, recently calculates protection ratio according to the peak integration of carboxylate and carboxylic acid, and result is 100%.

[R3's is synthetic]

Synthesizing of polyamic acid (polyimide precursor)

In possessing the 300mL flask of thermometer, stirrer, nitrogen ingress pipe, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 8.49g, after being dissolved in METHYLPYRROLIDONE 108.75g, under ice bath is cooling, at 2 ℃, add (1R, 2S, 4S, 5R)-cyclohexane tetracarboxylic dianhydride (manufacture, PMDA-HS) 10.70g by rock paddy gas (thigh).At 4 ℃, react 1 hour, then at 25 ℃, react after 12 hours, add phthalic anhydride 1.62g, at room temperature stir 2 hours.In this polyamic acid solution, add NMP109g and carry out coolingly, at 0 ℃ of following chloromethyl methyl ether 10.10g that adds, then add DIPEA 12.97g.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1500ml, will separates out solid leaching, dry, obtain object (resin R3) 22.3g of white solid.If utilize GPC to analyze the resin of gained, Mw=1.93 * 10 ⁴, Mw/Mn=1.82.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-110's is synthetic]

In possessing the 100mL flask of thermometer, stirrer, calcium chloride tube, add 1,1,2-trimethoxy-ethane 48.0g, acetyl chloride 29.8g, zinc chloride 10mg, at room temperature react 8 hours, obtains as the represented compound 76.3g of the following structure (b5-1) of transparency liquid.

[changing 100]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 125.8g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP62.3g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 17.71g, adds the above-mentioned transparency liquid 27.69g about the represented compound of said structure (b5-1) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1.2L, will separates out solid leaching, dry, obtain object (resin P-110) 22.71g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.52 * 10 ⁴, Mw/Mn=1.91.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

Resin P-110 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 206 ℃, and weight slip is 34%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 206 ℃.

[P-111's is synthetic]

In the 500mL flask that possesses thermometer, stirrer, Dien-Rodney Stark device, recirculatory pipe, add 1,1,2-trimethoxy-ethane 60.0g, 2-methyl cellosolve 190.0g, 10-camphorsulfonic acid 1.74g, hexane 200mL, reflux 48 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 3.79g, at 0 ℃, stir after 30 minutes, utilize ethyl acetate and saturated sodium bicarbonate water to extract.The organic layer of gained is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, under reduced pressure concentrated, obtain transparency liquid 97.2g.

In possessing the 300mL flask of thermometer, stirrer, calcium chloride tube, add above-mentioned solution 97.2g, acetyl chloride 43.0g, zinc chloride 10mg, at room temperature react after 8 hours, under reduced pressure concentrated, obtain as the represented compound 93.8g of the following structure (b5-2) of transparency liquid.

[changing 101]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 125.8g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP62.3g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 16.60g, adds the above-mentioned transparency liquid 33.07g about the represented compound of said structure (b5-2) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1.5L, will separates out solid leaching, dry, obtain object (resin P-111) 23.86g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.62 * 10 ⁴, Mw/Mn=1.62.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 99%.

Resin P-111 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 210 ℃, and weight slip is 42%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 210 ℃.

[P-112's is synthetic]

In the 1L flask that possesses thermometer, stirrer, Dien-Rodney Stark device, recirculatory pipe, add 1,1,2-trimethoxy-ethane 150.0g, 2-phenoxetol 379.5g, 10-camphorsulfonic acid 4.35g, hexane 200mL, reflux 48 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 9.47g, at 0 ℃, stir after 30 minutes, utilize ethyl acetate and saturated sodium bicarbonate water to extract.The organic layer of gained is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, under reduced pressure concentrated, obtain transparency liquid 532.4g.

In possessing the 1L flask of thermometer, stirrer, calcium chloride tube, add above-mentioned solution 532.4g, acetyl chloride 117.6g, zinc chloride 10mg, at room temperature react after 4 hours, under reduced pressure concentrated, obtain as the represented compound 518.2g of the following structure (b5-3) of transparency liquid.

[changing 102]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 260.4g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP129.2g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 36.55g, adds the above-mentioned transparency liquid 216.87g about the represented compound of said structure (b5-3) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 3L, will separates out solid leaching, dry, obtain object (resin P-112) 68.68g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.56 * 10 ⁴, Mw/Mn=1.85.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 97%.

Resin P-112 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 211 ℃, and weight slip is 51%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 211 ℃.

[P-113's is synthetic]

In the 500mL flask that possesses thermometer, stirrer, Dien-Rodney Stark device, recirculatory pipe, add 1,1,2-trimethoxy-ethane 50.0g, cyclohexanol 91.7g, 10-camphorsulfonic acid 1.45g, hexane 200mL, reflux 48 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 3.16g, at 0 ℃, stir after 30 minutes, utilize ethyl acetate and saturated sodium bicarbonate water to extract.The organic layer of gained is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, under reduced pressure concentrated, obtain transparency liquid 84.4g.

In possessing the 200mL flask of thermometer, stirrer, calcium chloride tube, add above-mentioned solution 84.4g, acetyl chloride 31.0g, zinc chloride 10mg, at room temperature react after 4 hours, under reduced pressure concentrated, obtain as the represented compound 91.2g of the following structure (b5-4) of transparency liquid.

[changing 103]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 125.8g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP62.3g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 16.60g, adds the above-mentioned transparency liquid 43.66g about the represented compound of said structure (b5-4) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1.5L, will separates out solid leaching, dry, obtain object (resin P-113) 26.40g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.52 * 10 ⁴, Mw/Mn=1.64.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 88%.

Resin P-113 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 177 ℃, and weight slip is 46%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 177 ℃.

[P-114's is synthetic]

In possessing the 500mL flask of thermometer, stirrer, calcium chloride tube, add iso-butyraldehyde 50.0g, magnesium sulfate 50.0g, methyl alcohol 200mL, 10-camphorsulfonic acid 1.61g, at 50 ℃, react 8 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 3.51g, at 0 ℃, stir 30 minutes.Magnesium sulfate is filtered, utilize hexane and saturated sodium bicarbonate water to extract filtrate.The organic layer of gained is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, concentrated under normal pressure, obtain transparency liquid 58.3g.

In possessing the 500mL flask of thermometer, stirrer, calcium chloride tube, add above-mentioned solution 58.3g, acetyl chloride 42.0g, zinc chloride 10mg, at 50 ℃, react 24 hours, obtain as the represented compound 81.0g of the following structure (b5-5) of transparency liquid.

[changing 104]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 125.8g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP62.3g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 22.14g, adds the above-mentioned transparency liquid 33.16g about the represented compound of said structure (b5-5) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1.5L, will separates out solid leaching, dry, obtain object (resin P-114) 20.12g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.28 * 10 ⁴, Mw/Mn=1.74.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 91%.

Resin P-114 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 163 ℃, and weight slip is 32%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 163 ℃.

[P-115's is synthetic]

In possessing the 500mL flask of thermometer, stirrer, calcium chloride tube, add iso-butyraldehyde 50.0g, magnesium sulfate 77.8g, 2-methyl cellosolve 158.3g, 10-camphorsulfonic acid 1.61g, at 50 ℃, react 10 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 3.51g, at 0 ℃, stir 30 minutes.Magnesium sulfate is filtered, utilize ethyl acetate and saturated sodium bicarbonate water to extract filtrate.The organic layer of gained is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, under reduced pressure concentrated, obtain transparency liquid 105.9g.

In possessing the 500mL flask of thermometer, stirrer, calcium chloride tube, add above-mentioned solution 105.9g, acetyl chloride 48.3g, at room temperature react after 4 hours, under reduced pressure concentrated, obtain as the represented compound 111.1g of the following structure (b5-6) of transparency liquid.

[changing 105]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 125.8g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP62.3g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 22.14g, adds the above-mentioned transparency liquid 35.80g about the represented compound of said structure (b5-6) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1.5L, will separates out solid leaching, dry, obtain object (resin P-115) 19.76g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.64 * 10 ⁴, Mw/Mn=1.62.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

Resin P-115 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 164 ℃, and weight slip is 42%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 164 ℃.

[P-118's is synthetic]

In possessing the 1L flask of thermometer, stirrer, calcium chloride tube, add 2-hydrocinnamicaldehyde 120.0g, magnesium sulfate 120.0g, methyl alcohol 600mL, 10-camphorsulfonic acid 2.08g, at 50 ℃, react 11 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 4.53g, at 0 ℃, stir 30 minutes.Magnesium sulfate is filtered, utilize ethyl acetate and saturated sodium bicarbonate water to extract filtrate.The organic layer of gained is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, under reduced pressure concentrated, obtain transparency liquid 144.2g.

In possessing the 1L flask of thermometer, stirrer, calcium chloride tube, add above-mentioned solution 144.2g, acetyl chloride 84.2g, at room temperature react after 2 hours, under reduced pressure concentrated, obtain as the represented compound 132.2g of the following structure (b5-9) of transparency liquid.

[changing 106]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 250.0g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP124.0g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 28.51g, adds the above-mentioned transparency liquid 40.82g about the represented compound of said structure (b5-9) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 2.7L, will separates out solid leaching, dry, obtain object (resin P-118) 66.54g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.43 * 10 ⁴, Mw/Mn=2.13.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 99%.

Resin P-118 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 165 ℃, and weight slip is 44%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 165 ℃.

[P-120's is synthetic]

In possessing the 300mL flask of thermometer, stirrer, calcium chloride tube, add 2-hydrocinnamicaldehyde 59.8g, magnesium sulfate 50.0g, 2-methyl cellosolve 101.8g, 10-camphorsulfonic acid 1.04g, at 50 ℃, react 12 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 2.26g, at 0 ℃, stir 30 minutes.Magnesium sulfate is filtered, utilize ethyl acetate and saturated sodium bicarbonate water to extract filtrate.The organic layer of gained is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, under reduced pressure concentrated, obtain transparency liquid 91.6g.

In possessing the 300mL flask of thermometer, stirrer, calcium chloride tube, add above-mentioned solution 91.6g, acetyl chloride 42.0g, at room temperature react after 2 hours, under reduced pressure concentrated, obtain as following (b5-10) of transparency liquid represented compound 97.1g.

[changing 107]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 125.0g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP62.0g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 16.45g, adds the above-mentioned transparency liquid 68.97g about the represented compound of said structure (b5-10) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1.5L, will separates out solid leaching, dry, obtain object (resin P-120) 29.96g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.44 * 10 ⁴, Mw/Mn=1.67.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 96%.

Resin P-120 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 162 ℃, and weight slip is 50%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 162 ℃.And then, at 198 ℃, also observe the endothermic peak that can be considered acid imide closed loop.

[P-122's is synthetic]

In possessing the 500mL flask of thermometer, stirrer, calcium chloride tube, add 2-hydrocinnamicaldehyde 120.0g, magnesium sulfate 100.0g, 2-propoxyl group ethanol 204.9g, 10-camphorsulfonic acid 2.08g, at 50 ℃, react 12 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 4.53g, at 0 ℃, stir 30 minutes.Magnesium sulfate is filtered, utilize ethyl acetate and saturated sodium bicarbonate water to extract filtrate.The organic layer of gained is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, under reduced pressure concentrated, obtain transparency liquid.

In possessing the 1L flask of thermometer, stirrer, calcium chloride tube, add total amount, the acetyl chloride 84.2g of above-mentioned solution, at room temperature react after 2 hours, under reduced pressure concentrated, obtain as the represented compound 211.7g of the following structure (b5-11) of transparency liquid.

[changing 108]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 260.4g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP129.2g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 36.55g, adds the above-mentioned transparency liquid 173.21g about the represented compound of said structure (b5-11) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 3L, will separates out solid leaching, dry, obtain object (resin P-122) 64.02g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.71 * 10 ⁴, Mw/Mn=1.82.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

Resin P-122 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 163 ℃, and weight slip is 54%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 163 ℃.And then also observe at 206 ℃ the endothermic peak that can be considered acid imide closed loop.

[P-127's is synthetic]

In possessing the 500mL flask of thermometer, stirrer, calcium chloride tube, add trimethyl-acetaldehyde 39.2g, magnesium sulfate 40.0g, methyl alcohol 50mL, hexane 200mL, 10-camphorsulfonic acid 1.06g, at 50 ℃, react 12 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 2.30g, at 0 ℃, stir 30 minutes.Magnesium sulfate is filtered, utilize hexane and saturated sodium bicarbonate water to extract filtrate.The organic layer of gained is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, concentrated under normal pressure, obtain transparency liquid 82.1g.

In possessing the 200mL flask of thermometer, stirrer, calcium chloride tube, add above-mentioned solution 76.6g, acetyl chloride 17.0g, zinc chloride 10mg, at 50 ℃, react 12 hours, obtain as the represented compound 112.0g of the following structure (b5-14) of transparency liquid.

[changing 109]

Similarly carry out the synthetic of polyamic acid with P-41, this polyamic acid solution 125.8g is added to possess thermometer, in the 300mL flask of stirrer, nitrogen ingress pipe, add NMP62.3g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 17.71g, adds the above-mentioned transparency liquid 51.47g about the represented compound of said structure (b5-14) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in methyl alcohol 1.5L, will separates out solid leaching, dry, obtain object (resin P-127) 15.27g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.57 * 10 ⁴, Mw/Mn=1.57.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

Resin P-127 is carried out to the analysis of differential thermobalance, and result heat absorption summit temperature is 230 ℃, and weight slip is 37%.This weight slip is equivalent to the R in the represented repetitive of general formula (1) ³weight, learn R ³heat decomposition temperature be 230 ℃.

[P-130's is synthetic]

Synthesizing of polyamic acid

In possessing the 1L flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 20.96g, after being dissolved in NMP (METHYLPYRROLIDONE) 628.8g, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 90.00g.Till stirring at 60 ℃ 4 hours and place and being cooled to room temperature.Then add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 27.27g, NMP154.6g also stirs 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 3.63g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=2.44 * 10 ⁴, Mn=0.95 * 10 ⁴, Mw/Mn=2.58.

Synthesizing of poly amic acid ester

This polyamic acid solution 246.71g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP122.87g and carry out cooling, at 0 ℃ of following DIPEA 27.96g that adds, then add the liquid 40.04g of (b5-9) synthetic in P-118.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 2.6L, will separates out solid leaching, dry, obtain object (resin P-130) 62.92g of white solid.If utilize GPC to analyze the resin of gained, Mw=3.33 * 10 ⁴, Mw/Mn=2.02.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 99%.

[P-131's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-130, this polyamic acid solution 246.71g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP122.87g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 27.96g, adds in P-122 the liquid 112.94g of synthetic (b5-11) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.1L, will separates out solid leaching, dry, obtain object (resin P-131) 70.16g of white solid.If utilize GPC to analyze the resin of gained, Mw=3.85 * 10 ⁴, Mw/Mn=1.90.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 99%.

[P-132's is synthetic]

Synthesizing of polyamic acid

In possessing the 1L flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 20.96g, after being dissolved in NMP (METHYLPYRROLIDONE) 628.8g, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 90.00g.Till stirring at 60 ℃ 4 hours and place and being cooled to room temperature.Then, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 25.98g, NMP147.2g stir 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 1.81g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=3.04 * 10 ⁴, Mn=1.19 * 10 ⁴, Mw/Mn=2.55.

Synthesizing of poly amic acid ester

This polyamic acid solution 243.92g is put into the 1L flask that possesses thermometer, stirrer, nitrogen ingress pipe, add NMP121.72g and carry out cooling, at 0 ℃ of following DIPEA 27.41g that adds, then add the liquid 39.25g of (b5-9) synthetic in P-118.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 2.6L, will separates out solid leaching, dry, obtain object (resin P-132) 61.84g of white solid.If utilize GPC to analyze the resin of gained, Mw=4.12 * 10 ⁴, Mw/Mn=2.35.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-133's is synthetic]

Similarly carry out the synthetic of polyamic acid with P-132, this polyamic acid solution 243.92g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP121.72g and carry out cooling, at 0 ℃ of following N that adds, N-diisopropylethylamine 27.41g, adds in P-122 the liquid 110.72g of synthetic (b5-11) then.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3L, will separates out solid leaching, dry, obtain object (resin P-133) 71.19g of white solid.If utilize GPC to analyze the resin of gained, Mw=4.79 * 10 ⁴, Mw/Mn=1.98.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 99%.

[P-134's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 10.48g, 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 14.61g, after being dissolved in NMP (METHYLPYRROLIDONE) 397.2g, interpolation 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 45.00g.Till stirring at 60 ℃ 6 hours and place and being cooled to room temperature.Add phthalic anhydride 4.53g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=2.10 * 10 ⁴, Mn=0.76 * 10 ⁴, Mw/Mn=2.77.

In possessing the 1L flask of thermometer, stirrer, calcium chloride tube, add 2-hydrocinnamicaldehyde 240.0g, magnesium sulfate 240.0g, 2-propoxyl group ethanol 558.9g, p-toluenesulfonic acid monohydrate 17.01g, at room temperature react 12 hours.Reactant liquor is cooled to till 0 ℃, adds triethylamine 45.25g, at 0 ℃, stir 30 minutes.Add ethyl acetate 500mL, add distilled water 1L and magnesium sulfate is dissolved completely.After separatory, organic layer is cleaned with distilled water, saturated aqueous common salt, after being dried with sodium sulphate, under reduced pressure concentrated, obtain transparency liquid 657.8g.

In possessing the 1L flask of thermometer, stirrer, calcium chloride tube, add aforesaid liquid 652.8g, acetyl chloride 168.5g, at room temperature react after 4 hours, under reduced pressure concentrated, the transparency liquid 716.6g of acquisition (b5-11).

Synthesizing of poly amic acid ester

Polyamic acid solution 251.63g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP124.6g and carry out cooling, at 0 ℃ of following DIPEA 28.78g that adds, then add the liquid 111.05g of above-mentioned (b5-11).0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.1L, will separates out solid leaching, dry, obtain object (resin P-134) 73.69g of white solid.If utilize GPC to analyze the resin of gained, Mw=3.21 * 10 ⁴, Mw/Mn=1.86.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 99%.

[P-135's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 10.48g, 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 13.64g, after being dissolved in NMP (METHYLPYRROLIDONE) 391.7g, interpolation 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 45.00g.Till stirring at 60 ℃ 6 hours and place and being cooled to room temperature.Add phthalic anhydride 1.81g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=3.46 * 10 ⁴, Mn=1.25 * 10 ⁴, Mw/Mn=2.76.

Synthesizing of poly amic acid ester

This polyamic acid solution 251.85g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP125.4g and carry out cooling, at 0 ℃ of following DIPEA 28.54g that adds, then add the liquid 110.43g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.1L, will separates out solid leaching, dry, obtain object (resin P-135) 74.57g of white solid.If utilize GPC to analyze the resin of gained, Mw=5.49 * 10 ⁴, Mw/Mn=2.02.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, recently calculates protection ratio according to the peak integration of carboxylate and carboxylic acid, and result is 99%.

[P-136's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 10.48g, 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 13.31g, after being dissolved in NMP (METHYLPYRROLIDONE) 389.8g, interpolation 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 45.00g.Till stirring at 60 ℃ 6 hours and place and being cooled to room temperature.Add phthalic anhydride 0.91g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=5.71 * 10 ⁴, Mn=2.07 * 10 ⁴, Mw/Mn=2.76.

Synthesizing of poly amic acid ester

This polyamic acid solution 255.29g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP127.4g and carry out cooling, at 0 ℃ of following DIPEA 28.84g that adds, then add the liquid 111.57g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.1L, will separates out solid leaching, dry, obtain object (resin P-136) 78.88g of white solid.If utilize GPC to analyze the resin of gained, Mw=8.58 * 10 ⁴, Mw/Mn=2.09.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-138's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 6.99g, after being dissolved in NMP (METHYLPYRROLIDONE) 294.6g, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 45.00g.Till stirring at 60 ℃ 4 hours and place and being cooled to room temperature.Then, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 20.78g, NMP117.8g also stirs 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 3.63g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=1.82 * 10 ⁴, Mn=0.71 * 10 ⁴, Mw/Mn=2.55.

Synthesizing of poly amic acid ester

This polyamic acid solution 260.66g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP129.4g and carry out cooling, at 0 ℃ of following DIPEA 28.51g that adds, then add the liquid 110.22g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.2L, will separates out solid leaching, dry, obtain object (resin P-138) 72.98g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.76 * 10 ⁴, Mw/Mn=1.79.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 99%.

[P-139's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 8.73g, after being dissolved in NMP (METHYLPYRROLIDONE) 304.5g, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 45.00g.Till stirring at 60 ℃ 4 hours and place and being cooled to room temperature.Then, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 17.53g, NMP99.4g stir 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 3.63g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=1.68 * 10 ⁴, Mn=0.65 * 10 ⁴, Mw/Mn=2.58.

Synthesizing of poly amic acid ester

This polyamic acid solution 255.32g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP126.7g and carry out cooling, at 0 ℃ of following DIPEA 28.51g that adds, then add the liquid 110.22g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.2L, will separates out solid leaching, dry, obtain object (resin P-139) 71.56g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.67 * 10 ⁴, Mw/Mn=1.78.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 98%.

[P-141's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 13.04g, after being dissolved in NMP (METHYLPYRROLIDONE) 345.9g, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 48.00g.Till stirring at 60 ℃ 4 hours and place and being cooled to room temperature.Then, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 11.78g, NMP66.7g stir 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 3.87g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=1.54 * 10 ⁴, Mn=0.53 * 10 ⁴, Mw/Mn=2.89.

Synthesizing of poly amic acid ester

This polyamic acid solution 254.85g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP126.4g and carry out cooling, at 0 ℃ of following DIPEA 29.69g that adds, then add the liquid 114.82g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.2L, will separates out solid leaching, dry, obtain object (resin P-141) 73.07g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.52 * 10 ⁴, Mw/Mn=1.76.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-142's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 15.21g, after being dissolved in NMP (METHYLPYRROLIDONE) 363.9g, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 49.00g.Till stirring at 60 ℃ 4 hours and place and being cooled to room temperature.Then, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 8.49g, NMP48.1g stir 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 3.95g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=1.56 * 10 ⁴, Mn=0.52 * 10 ⁴, Mw/Mn=2.99.

Synthesizing of poly amic acid ester

This polyamic acid solution 249.29g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP123.6g and carry out cooling, at 0 ℃ of following DIPEA 29.69g that adds, then add the liquid 114.82g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.2L, will separates out solid leaching, dry, obtain object (resin P-142) 73.21g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.65 * 10 ⁴, Mw/Mn=1.78.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-143's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 17.47g, after being dissolved in NMP (METHYLPYRROLIDONE) 382.3g, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 50.00g.Till stirring at 60 ℃ 4 hours and place and being cooled to room temperature.Then, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 5.05g, NMP28.6g stir 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 4.03g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=1.54 * 10 ⁴, Mn=0.41 * 10 ⁴, Mw/Mn=3.73.

Synthesizing of poly amic acid ester

This polyamic acid solution 243.73g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP120.9g and carry out cooling, at 0 ℃ of following DIPEA 29.69g that adds, then add the liquid 114.57g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.2L, will separates out solid leaching, dry, obtain object (resin P-143) 72.50g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.68 * 10 ⁴, Mw/Mn=1.80.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-144's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 10.48g, is dissolved in NMP (METHYLPYRROLIDONE) 314.4g.Be heated to 70 ℃, interpolation 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 15.00g stirs 15 minutes at 70 ℃.Further interpolation 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride 15.00g stirs 15 minutes at 70 ℃.Further add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride 15.00g, till stirring at 60 ℃ 4 hours and place and being cooled to room temperature.Then, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 14.29g, NMP81.0g stir 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 3.63g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=1.50 * 10 ⁴, Mn=0.60 * 10 ⁴, Mw/Mn=2.50.

Synthesizing of poly amic acid ester

This polyamic acid solution 249.99g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP124.0g and carry out cooling, at 0 ℃ of following DIPEA 28.51g that adds, then add the liquid 107.22g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.1L, will separates out solid leaching, dry, obtain object (resin P-144) 72.20g of white solid.If utilize GPC to analyze the resin of gained, Mw=2.39 * 10 ⁴, Mw/Mn=1.76.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-145's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 45.00g, NMP (METHYLPYRROLIDONE) 234.4g, one side stirs one side and is heated to 70 ℃.To in NMP80g, be dissolved with anti-form-1 with 30 minutes, after the solution that 4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 10.48g forms drops in above-mentioned flask, till stirring 4 hours and place and being cooled to room temperature at 60 ℃.Then, add 2,2 '-dimethyl-4,4 '-benzidine (Wakayama refine (thigh) manufacture) 14.29g, NMP81.0g stir 2 hours at 60 ℃.Till placement is cooled to room temperature, add phthalic anhydride 3.63g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=1.21 * 10 ⁴, Mn=0.47 * 10 ⁴, Mw/Mn=2.58.

Synthesizing of poly amic acid ester

This polyamic acid solution 249.99g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP124.0g and carry out cooling, at 0 ℃ of following DIPEA 28.51g that adds, then add the liquid 107.22g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.1L, will separates out solid leaching, dry, obtain object (resin P-145) 67.95g of white solid.If utilize GPC to analyze the resin of gained, Mw=1.94 * 10 ⁴, Mw/Mn=1.69.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

[P-146's is synthetic]

Synthesizing of polyamic acid

In possessing the 500mL flask of thermometer, stirrer, nitrogen ingress pipe, add 3,3 ', 4,4 '-biphenyltetracarboxyacid acid acid anhydride (Mitsubishi Chemical's (thigh) manufacture) 45.00g, NMP (METHYLPYRROLIDONE) 265.3g, one side stirs one side and is heated to 70 ℃.With 30 minutes, will in NMP130g, be dissolved with anti-form-1,4-cyclohexane diamine (rock paddy gas (thigh) manufacture) 10.48g, 2,2 '-dimethyl-4, after the solution that 4 '-benzidine (Wakayama refine (thigh) manufacture) 14.29g forms drops in above-mentioned flask, till stirring at 60 ℃ 6 hours and place and being cooled to room temperature.Then, add phthalic anhydride 3.63g, at room temperature stir 10 hours and obtain the transparent polyamic acid solution of brown slightly.If utilize GPC to analyze the solution of gained, Mw=2.26 * 10 ⁴, Mn=0.85 * 10 ⁴, Mw/Mn=2.65.

Synthesizing of poly amic acid ester

This polyamic acid solution 249.99g is added to possess thermometer, in the 1L flask of stirrer, nitrogen ingress pipe, add NMP124.0g and carry out cooling, at 0 ℃ of following DIPEA 28.51g that adds, then add the liquid 107.22g of (b5-11) synthetic in P-134.0 ℃ of following reaction, after 4 hours, reactant liquor is added in isopropyl alcohol 3.1L, will separates out solid leaching, dry, obtain object (resin P-146) 72.30g of white solid.If utilize GPC to analyze the resin of gained, Mw=3.75 * 10 ⁴, Mw/Mn=1.93.Dissolution of solid is also measured in deuterated DMSO ¹h-NMR spectrum, calculates protection ratio according to carboxylate and the peak integration ratio of carboxylic acid, and result is 100%.

Other resins are also similarly to synthesize.The quadrivalent organic radical R of the resin that these are synthetic ¹the monomer structure that peripheral structure is originated, divalent organic base R ²the diamine monomer of periphery, formation R ¹the monomer of peripheral structure and R ²the interpolation mol ratio of the diamine monomer of periphery, about R ³pass through sour effect occur to decompose produces alkali-soluble base base when the situation of use (and be mol ratio separately), this base to the protection ratio of carboxyl, end-capping reagent, synthetic method, quality mean molecular weight and dispersion degree (Mw/Mn) as described in following table 1～table 4.

Abbreviation in table is below shown.

[changing 110]

[changing 111]

[changing 112]

[changing 113]

[changing 114]

[changing 115]

[preparation of photosensitive polymer combination]

Composition shown in following table is dissolved in in the solvent shown in table, and making total solid constituent concentration is 25 quality %, and utilizing aperture is that the teflon box type filter processed of 0.1 μ m filters, and prepares photosensitive polymer combination.In table, with quality %, represent the solid component content of each composition.

The ageing stability > of < photosensitive polymer combination

The photosensitive polymer combination that makes embodiment 110 at room temperature through time 4 weeks after, the solution of composition is dissolved in deuterated DMSO and is measured ¹h-NMR spectrum, calculates acid imide rate according to the peak integration value of amide NH, and 32% through imidizate as a result.The photosensitive polymer combination that makes embodiment 122 at room temperature through time 4 weeks after, the solution of composition is dissolved in deuterated DMSO and is measured ¹h-NMR spectrum, calculates acid imide rate according to the peak integration value of amide NH, and result acid imide rate is less than 1%.

The photosensitive polymer combination that makes embodiment 114 at room temperature through time 4 weeks, the reduction of result colloidal viscosity.In addition, the acid number of photosensitive polymer combination is measured, result is the reduction of visible acid number also, and decomposition has occurred a part for the sour decomposability base that contains (a5-5) represented structure of resin P-114.The photosensitive polymer combination that makes embodiment 122 at room temperature through time 4 weeks, result has no the reduction of viscosity and acid number.

[image property evaluation]

By prepared photosensitive polymer combination rotary coating, on 4 inches of silicon wafers, the preparation of carrying out 3 minutes on hot plate at 120 ℃ is dry, obtains the film of thickness 5.0 μ m.Then, in i ray stepping exposure device FPA-3000i5+ (Canon (Canon) (thigh) manufacture), use the through hole repeat patterns shade of 1 μ m～30 μ m to carry out pattern exposure.Then at 120 ℃, heat 3 minutes, utilize tetramethyl ammonium hydroxide (Tetramethylammonium hydroxide, the TMAH) aqueous solution of 2.38 quality % to soak and put development, utilize pure water to carry out drip washing processing.100 ℃ on hot plate carry out heating in 2 minutes thereafter.

< resolution >

By surveying long scan formula electron microscope (Scanning Electron Microscopy, SEM) (Hitachi (thigh), S-8840) pattern film of gained is observed, the average evaluation that the minimum dimension of the resolve through hole of (resolve) is less than to 3 μ m is A, 3 μ m average evaluation above and that be less than 5 μ m is B, 5 μ m average evaluation above and that be less than 10 μ m is C, and average evaluations more than 10 μ m is D.

< sensitivity >

By surveying long SEM, (Hitachi (thigh), S-8840) observes the pattern film of gained, and the exposure that the through hole of minimum dimension is resolved, as sensitivity, will be less than 250mJ/cm ²average evaluation be A, by 250mJ/cm ²above and be less than 500mJ/cm ²average evaluation be B, by 500mJ/cm ²above and be less than 750mJ/cm ²average evaluation be C, by 750mJ/cm ²above average evaluation is D.

[membrane property evaluation]

Prepared photosensitive polymer combination rotary coating, on 4 inches of silicon wafers, is carried out to preparation in 3 minutes dry on hot plate at 120 ℃, obtain the film of thickness 5.0 μ m.Then heat hardening 60 minutes and obtain polyimide film at 250 ℃ under condition of nitrogen gas.

< stress >

Utilize the stress of membrane stress determinator (KLA-Tencor company manufacture, FLX-2320 type) at the film after solidifying is measured to 25 ℃.The value of stress is less, means that chip warpage amount is fewer.

In following table, and with the numeric representation mass ratio in the parantheses of the situation of solvent.

Abbreviation in table is below shown.

[acid producing agent]

[changing 116]

[sensitizer]

[changing 117]

[thermal acid generator]

[changing 118]

[alkali compounds]

DIA:2,6-diisopropyl aniline

PEA:N-phenyldiethanol-amine

DBU:1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene

EOA: the amine of following structure

[changing 119]

[interfacial agent]

F176:Megafac F176 (large Japanese ink chemical industry (thigh) is manufactured)

F475:Megafac F-475 (large Japanese ink chemical industry (thigh) is manufactured)

PF6320:(Ou Nuofa (OMNOVA) company manufactures, fluorine system)

BYK307:(Bi Ke chemistry (BYK Chemie) company manufactures)

[connecting airtight promoter]

GPTMS:3-glycidoxypropyltrimewasxysilane

MAPTMS:3-methacryloxypropyl trimethoxy silane

TESPEC: ethyl carbamic acid triethoxysilicane alkyl propyl ester

[solvent]

GBL: gamma-butyrolacton

NMP:N-methyl pyrrolidone

CX: cyclohexanone

CP: cycloheptanone

DMI:1,3-dimethyl-2-imidazolinone

[polymerizable compound]

DPHA: dipentaerythritol acrylate

By the result shown in table 5～table 8, clearly learnt to there is sour decomposability base as the R in general formula (1) ³but do not there is alicyclic group as R ²the dissolubility of 1 pair of alkaline developer of comparative example low, about image properties such as resolution, sensitivity, cannot obtain sufficient result.Learn in addition, stress also may produce chip warpage greatly.

About alicyclic group, there is alicyclic group as R ²but do not there is sour decomposability base as R ³comparative example 2, learn that sub-image is also not obvious, about image properties such as resolution, sensitivity, cannot obtain sufficient result.Learn in addition, stress also may produce chip warpage greatly.

About thering is sour decomposability base as the R in general formula (1) ³but do not there is alicyclic group as R ²comparative example 3, although the image properties such as the resolution of learning, sensitivity are relatively good, stress is large and may produce chip warpage.

Learn on the other hand, use the image properties such as resolution, sensitivity of embodiment 1～embodiment 146 of resin (a) of the important document meet general formula (1) excellent, stress generation also little and chip warpage is also inhibited.

Utilizability in industry

According to the present invention; the semiconductor device that can provide a kind of relief pattern to form material, photosensitive film, polyimide film, sclerosis relief pattern, its manufacture method and contain this sclerosis relief pattern; above-mentioned relief pattern forms the interlayer dielectric that material can suitably be used as surface protection film, interlayer dielectric, the display element of semiconductor device; micro-shadow performance with resolution and sensitivity excellence; low stress excellent under low-temperature setting, can form the sclerosis relief pattern that prevents chip warpage.

The present invention is illustrated in detail and with reference to specific embodiment, but dealer should be clear and definite, can be in the situation that not departing from spirit of the present invention and scope in addition various changes or correction.

The Japanese patent application case (Japanese patent application case 2012-068197) of filing an application in the Japanese patent application case that the application's case was filed an application based on July 29th, 2011 (Japanese patent application case 2011-167622) and on March 23rd, 2012, is incorporated to its content herein by reference.

Claims

1. a photosensitive polymer combination, is characterized in that containing:

(a) have the represented repetitive of following general formula (1) resin and

(b) the acidic compound by the irradiation of active ray or radioactive ray,

[changing 1]

In described general formula (1),

R ³independently represent respectively hydrogen atom or organic group;

2. photosensitive polymer combination according to claim 1, it is characterized in that, there is the resin (a) of the represented repetitive of described general formula (1) for thering is the resin of the represented repetitive of the represented repetitive of following general formula (2) and following general formula (3)

[changing 2]

In described general formula (2),

R ¹' with described general formula (1) in R ¹for identical meanings;

R ³' with described general formula (1) in R ³for identical meanings;

R ⁴for containing the divalent organic base of alicyclic group;

In described general formula (3),

R ¹" with the R in described general formula (1) ¹for identical meanings;

R ³" with the R in described general formula (1) ³for identical meanings;

R ⁵for with R ⁴different divalent organic bases.

3. photosensitive polymer combination according to claim 2, is characterized in that, the R in described general formula (3) ⁵for containing the bivalent radical of aromatic series base.

4. photosensitive polymer combination according to claim 3, is characterized in that, the R in described general formula (3) ⁵for any represented bivalent radical of following formula,

[changing 3]

In described formula, the hydrogen atom of each aromatic rings can be respectively independently at least one atom or the base in selecting the cohort that free fluorine atom, chlorine atom, bromine atoms, methyl, methoxyl, cyano group, phenyl and trifluoromethyl form replace.

5. according to the photosensitive polymer combination described in any one in claim 1 to 4, it is characterized in that, in described general formula (1)-CO ₂r ³, in described general formula (2)-CO ₂r ³' or described general formula (3) in-CO ₂r ³" heat decomposition temperature be 100 ℃～220 ℃.

6. according to the photosensitive polymer combination described in any one in claim 1 to 5, it is characterized in that, in described general formula (1)-CO ₂r ³, in described general formula (2)-CO ₂r ³' or described general formula (3) in-CO ₂r ³" the sour effect passed through occur to decompose and produce the ester group that hydrogen atom that the base of alkali-soluble base is carboxyl forms through the represented base replacement of following general formula (III),

[changing 4]

In described general formula,

Ra represents hydrogen atom, alkyl, naphthenic base, aryl or aralkyl;

Rb represents singly-bound or bivalence linking base;

Ra, Rb and Q at least two also bonds and form ring mutually.

7. photosensitive polymer combination according to claim 6, is characterized in that, the Ra in described general formula (III) is following general formula (IV) or the represented base of general formula (V),

[changing 5]

In described general formula,

8. photosensitive polymer combination according to claim 7, it is characterized in that, the Rc in described general formula (IV) and at least one of Rd are naphthenic base, aryl, aralkyl, alkoxy, aryloxy group, alkoxy carbonyl, aryloxycarbonyl, cyano group or halogen atom.

9. photosensitive polymer combination according to claim 8, is characterized in that, the Rc in described general formula (IV) and at least one of Rd are aryl.

10. photosensitive polymer combination according to claim 6, is characterized in that, Ra, the Rb in described general formula (III) and at least one of Q are electrophilic base or the base that contains electrophilic base.

11. photosensitive polymer combinations according to claim 1, is characterized in that, the R in described general formula (1) ¹for the fatty group that contains monocyclic or condensation polycyclic formula or the tetravalence concatenating group of aromatic series base.

12. according to the photosensitive polymer combination described in claim 1 or 11, it is characterized in that the R in described general formula (1) ²for the bivalent radical that contains alicyclic group, the bivalent radical that contains aromatic series base or the bivalent radical that contains silicon atom.

13. according to the photosensitive polymer combination described in any one in claim 1 to 12, it is characterized in that, the quality mean molecular weight of described resin (a) is below 200,000.

14. according to the photosensitive polymer combination described in any one in claim 1 to 13, it is characterized in that, also contains (c) alkali compounds.

15. according to the photosensitive polymer combination described in any one in claim 1 to 14, it is characterized in that, described compound (b) is oxime compound.

16. according to the photosensitive polymer combination described in any one in claim 1 to 15, it is characterized in that, also contains (f) and connects airtight promoter.

17. the photosensitive polymer combination according to described in any one in claim 1 to 16, is characterized in that, it develops and uses for eurymeric.

18. a pattern forming material, is characterized in that, it is the photosensitive polymer combination as described in any one in claim 1 to 16.

19. 1 kinds of photosensitive films, is characterized in that, it is to form by the photosensitive polymer combination as described in any one in claim 1 to 16.

20. 1 kinds of polyimide films, is characterized in that, it is that the photosensitive polymer combination as described in any one in claim 1 to 16 is carried out heat treated and obtained.

The manufacture method of 21. 1 kinds of relief patterns that harden, is characterized in that, comprising:

(A) on substrate, form the step of photosensitive film as claimed in claim 19;

(B) step of utilizing active ray or radioactive ray to expose to described photosensitive film;

(C) step that the mode of in order to use alkaline developer, described photosensitive film being removed through the part of exposure is developed; And

(D) relief pattern of gained is carried out to the step of heat treated.

22. 1 kinds of sclerosis relief patterns, is characterized in that, it is that manufacture method by sclerosis relief pattern as claimed in claim 21 obtains.

23. 1 kinds of semiconductor devices, is characterized in that, possess sclerosis relief pattern as claimed in claim 22.

24. a resin, is characterized in that, has the represented repetitive of following general formula (1),

[changing 6]

In described general formula (1),

R ³independently represent respectively hydrogen atom or organic group;